Polyolefin elastomer with improved processability and curing time

Abstract

The embodiments relate to a method for producing a rheology-modified polyolefin elastomer, the method comprising the step of forming a first composition comprising: a density of 0.860 to 0.900 g / cc; a melt index (I2) of 0.5 to 50 dg / min (wherein I2 is measured according to ASTM D1238 (190°C, 2.16 kg)); and a polyolefin elastomer having at least 0.2 vinyls per 1000 carbons; and an organic peroxide of 0.01 wt% to 0.3 wt% based on the combined weight of the polyolefin elastomer and the organic peroxide. Further embodiments relate to a rheology-modified polyolefin elastomer produced using this process. Further embodiments relate to crosslinkable polyolefin elastomer formulations and crosslinked polyolefin elastomers and articles produced therefrom.

Description

Technology Field

[0001] The embodiments of the present disclosure generally relate to polyolefin elastomers and methods for producing the same, and more specifically, rheology-modified polyolefin elastomers and methods for producing the same. Background Technology

[0002] Polyolefin elastomers with shear thinning rheology and efficient peroxide curing reactions (high degree of curing and short curing times) are desirable for applications such as photovoltaic (PV) encapsulation films, shoe foams, and wiring and cable compounds, and must meet various other requirements. For example, to prevent movement of electrical components and wiring within photovoltaic modules, polymeric encapsulation materials must not flow significantly at temperatures up to 85°C. One way to achieve this is to use semicrystalline polymers with melting points exceeding this temperature. However, other encapsulation material requirements, such as high optical transparency and low modulus, are typically achieved with low-crystalline polymers. To balance these requirements, low-crystalline polymers, such as ethylene-vinyl acetate copolymer (EVA) or polyolefin elastomer (POE), e.g., ENGAGE™ Polyolefin Elastomer, are typically used in conjunction with peroxide-based reactive curing formulations. While low-crystalline polymers provide high transparency and low modulus, the curing formulation promotes crosslinking reactions, causing the polymer to form a network structure that provides mechanical stability at high temperatures. This crosslinking reaction typically occurs during module lamination, which is performed at 150°C.

[0003] When using peroxide-curing formulations, the film extrusion process must generally be performed at low temperatures to prevent the peroxide from decomposing in the extruder and initiating the crosslinking reaction. The heat generated during extrusion is related to the extrusion rate and polymer viscosity; higher viscosity and higher extrusion rates generate more heat. Therefore, to extrude "peroxide-cured" encapsulant films, low-viscosity resins are extruded at low speeds. However, low extrusion rates are economically disadvantageous, and low viscosity is typically achieved through the use of low-molecular-weight resins. Low-molecular-weight resins may not crosslink efficiently and may require a higher loading of peroxide in the curing formulation or a longer time in the module lamination process to reach the required level of crosslinking. Excess peroxide or adjuvant additives mixed with POE may migrate to the surface due to the low compatibility between the additives and the POE material, causing the film surface to become slippery; this is considered a major disadvantage of POE-based encapsulants compared to EVA-based or EVA-POE-EVA multilayer-based film designs.

[0004] Therefore, there is a continuous need for polyolefin elastomers that allow encapsulant materials to be extruded faster and cured more quickly with fewer curing additives to achieve the same degree of curing.

[0005] The embodiments of the present disclosure satisfy this need through the rheological modification of polyolefin elastomers having high vinyl levels, low oligomer levels, and high levels of long chain branching (LCB) at the polymer chain ends. LCB enhances polymer chain entanglement, and single side chains must be sufficiently longer than some critical molecular weight, which is expected to result in higher viscosity than polymers without LCB at low shear rates. However, LCB also reduces hydrodynamic volume, so polymers with long chain branching are more prone to unraveling than polymers without long chain branching but with similar molecular weights. Although these two factors are contradictory in their influence on polymer rheological properties, LCB polymers are expected to provide better shear thinning properties and an effective method for improving the processability of polyolefin elastomers.

[0006] Peroxide post-modification is one approach to introducing long-chain branches into linear ethylene copolymers. For conventional polyolefin elastomers, peroxide post-modification can increase shear thinning to some extent but generally slows down the peroxide curing rate. However, for the chain-end unsaturated polyolefin elastomers described herein, which have high vinyl levels and low oligomer levels at the polymer chain ends, rheological modification through peroxide post-treatment improves peroxide curing performance while also improving shear thinning characteristics. The rheologically modified polyolefin elastomers of this disclosure achieve a balance of peroxide curing, processability, and the possibility of using lower levels of curing additives to reach the required peroxide curing reaction.

[0007] According to one or more embodiments, a method for producing a rheology-modified polyolefin elastomer comprises the steps of forming a first composition comprising 0.01% by weight to 0.3% by weight of an organic peroxide based on the combined weight of the polyolefin elastomer and the organic peroxide, and decomposing at least 75% by weight of the organic peroxide in the first composition, wherein the polyolefin elastomer has a density of 0.860 to 0.900 g / cc, at least 0.2 vinyl per 1000 carbons, and a melt index (I2) of 0.5 to 50 dg / min.

[0008] In some embodiments, the polyolefin elastomer is prepared by solution polymerizing ethylene and optionally an α-olefin comonomer in the presence of a precatalyst having the following structure (I):

[0009]

[0010] In the above formula, M is Zr or Hf, and the metal is in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is an independently selected monodentate ligand; the total catalyst is charge-neutral; and R 1 and R 16 At least one of them is selected from the group consisting of structure (II), structure (III) and structure (IV):

[0011]

[0012] In structures (II), (III) and (IV), R 31-35 , R 41-48 and R 51-59 is -H, C1-C 40 Hydrocarbyl, C1-C 40 Heterohydrocarbil, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N)2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)- or independently selected from halogen, and R C is C1-C 40 Independently selected from hydrocarbil; R 3 and R 14 C1-C independently 40 Hydrocarbyl or hydrogen; R 6 and R 11 C1-C independently 40 Hydrocarbyl or hydrogen; R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 and R 15 is C1-C 40 Hydrocarbyl, C1-C 40 Heterohydrocarbyl, ―Si(R C )3, independently selected from the group consisting of halogen atoms, hydrogen atoms, and combinations thereof; R 17 and R 18 is independently C1-C3 hydrocarbylene; R 19 and R 20 C1-C independently 40 It is hydrocarbyl or hydrogen.

[0013] In some embodiments, the polyolefin elastomer is prepared using an Al-based chain transfer agent (CTA) beta-hydride removal technique.

[0014] Further embodiments relate to a crosslinkable polyolefin elastomer formulation comprising the rheology-modified polyolefin elastomer described herein and 0.1% to 2% by weight of the second organic peroxide based on the combined weight of the rheology-modified polyolefin elastomer and the second organic peroxide.

[0015] Additional features and benefits will be specified in the following detailed description, and in part will become readily apparent to those skilled in the art from such description or will be recognized by practicing the embodiments described herein, including the following detailed description and claims.

[0016] It should be understood that both the foregoing general description and the following detailed description are intended to describe various embodiments and to provide an overview or framework for understanding the nature and features of the claimed subject matter. Specific details for implementing the invention

[0017] Specific embodiments of the present application will now be described. The present disclosure may be implemented in different forms and should not be construed as being limited to the embodiments presented in the present disclosure. Rather, such embodiments are provided to ensure that the present disclosure is thorough and complete and will fully convey the scope of the subject matter to those skilled in the art.

[0018] definition

[0019] Unless otherwise specified, implied in the context, or customary in the art, all parts and percentages are based on weight, and all test methods are the most recent as of the filing date of this disclosure.

[0020] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. The general term "polymer" includes the term "homogeneous polymer" (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace impurities may be incorporated into the polymer structure) and the term "hybrid polymer" as defined below. Trace impurities, such as catalyst residues, may be incorporated into and / or within the polymer. Typically, the polymer is stabilized by one or more stabilizers in very small amounts ("ppm" amounts).

[0021] As used herein, the term "copolymer" refers to a polymer produced by the polymerization of at least two different types of monomers. Accordingly, the term "copolymer" includes the term copolymer (used to refer to a polymer produced from two different types of monomers) and a polymer produced from more than two different types of monomers.

[0022] The term “polyolefin” as used herein refers to a polymer comprising 50% by weight or most by weight of an olefin, such as ethylene or propylene, in a polymerized form (based on the weight of the polymer), and optionally may comprise one or more comonomers.

[0023] The terms “ethylene-based polymer” or “polyethylene” as used herein refer to a polymer comprising 50% by weight or most by weight of ethylene in a polymerized form (based on the weight of the polymer) and optionally comprising one or more comonomers.

[0024] The term "ethylene / alpha-olefin copolymer" as used herein refers to a copolymer comprising, in a polymerized form, 50 weight percent or most weight percent of ethylene and alpha-olefin as only two monomer types (based on the weight of the copolymer). Preferably, the ethylene / alpha-olefin copolymer is a random copolymer (i.e., containing a random distribution of monomer components).

[0025] As used herein, "unimodal" refers to a molecular weight distribution (MWD) represented by a gel permeation chromatography (GPC) curve exhibiting a single peak, the single peak being defined by a single positive inflection point where the derivative of the GPC curve for the MWD changes from positive to negative as log(molecular weight) increases within the range of 2 to 8, further ranging from 3 to 7. Preferably, the resin has an Mw / Mn of less than about 3.5, further less than 2.8. More preferably, the resin composition is the result of a single reactor, single catalyst polymerization process.

[0026] As used herein, the term “rheology-modified polyolefin elastomer” refers to a polyolefin elastomer that has undergone a reaction to increase the degree of long-chain branching. For example, a rheology-modified polyolefin elastomer may be formed by reacting a polyolefin elastomer with a peroxide, for example by melt blending, so that the peroxide acts as a rheology modifier, increasing the degree of long-chain branching (LCB) in the rheology-modified polyolefin elastomer to a degree greater than the degree of LCB in the basic polyolefin elastomer prior to peroxide modification, but without inducing crosslinking so that the rheology-modified polyolefin elastomer is still melt-processable (i.e., it is not thermosetting). As discussed in more detail below, non-limiting examples of suitable melt blending processes include batch mixing processes and continuous extrusion processes. The basic polyolefin elastomer may be an ethylene / alpha-olefin copolymer as described in detail below.

[0027] As used herein, the terms "crosslinked composition" or "crosslinked polyolefin elastomer" refer to a composition having a network structure due to the formation of chemical bonds between polymer chains. The degree of formation of this network structure is indicated by an increase in the "MH-ML" differential compared to a non-crosslinked composition. The crosslinked composition generally has a gel content of at least 50 wt%, additionally at least 60 wt%, additionally at least 70 wt%, and additionally at least 80 wt% based on the weight of the crosslinked composition. Refer to the gel test below.

[0028] The term “long chain branch” as used herein refers to a chain length longer than the chain length formed by incorporating a comonomer into a polymer backbone. Furthermore, the term “long chain branch” refers to a chain length having at least one more carbon than a short chain branch, and the term “short chain branch” as used herein refers to a chain length having two fewer carbons than the number of carbons in the comonomer. For example, an ethylene / 1-octene copolymer having short and long chain branches has a backbone having a long chain branch of at least seven (7) carbons, but this backbone also has a short chain branch of only six (6) carbons.

[0029] The term "independently selected," which involves multiple options, is R 1 , R 2 , R 3 , R 4 , R 5 and R C It indicates that individual R groups appearing before a term such as [ ] may be the same or different without depending on the identity of any other group appearing before that term.

[0030] The term "precatalyst" refers to a compound that exhibits catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with the precatalyst in a manner that converts the precatalyst into a catalytically active catalyst. As used herein, the terms "activating co-catalyst" and "activator" are interchangeable.

[0031] When describing a specific chemical group containing a carbon atom, "(C x -C y An interpolation expression of the form )" implies that the unsubstituted chemical group has x to y carbon atoms, including x and y. For example, (C1-C 30 )alkyl is an unsubstituted alkyl group having 1 to 30 carbon atoms. In some embodiments and general structures, a specific chemical group is R SIt can be substituted by one or more substituents such as. "(C x -C y R of a chemical group defined using the )" insertion S The substituted version is any R S Depending on the identity of the group, it can contain more than y carbon atoms. For example, "exactly one R S (C1-C 50 )alkyl(R S "is phenyl (-C6H5)" can contain 7 to 56 carbon atoms. Therefore, generally "(C x -C y )" A chemical group defined using the insertion is a substituent R containing one or more carbon atoms. S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is all carbon atom-containing substituents R S It is determined by adding the combined sum of the number of carbon atoms from to both x and y.

[0032] The term "substitution" refers to at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group being a substituent (e.g., R S It means being replaced by ). The term "persubstitution" refers to all hydrogen atoms (H) bonded to the carbon atom or heteroatom of the corresponding unsubstituted compound or functional group being replaced by a substituent (e.g., R S It means being replaced by ). The term "polysubstitution" means that at least two, but fewer than all, hydrogen atoms bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" refers to a hydrogen or hydrogen radical covalently bonded to another atom. When describing the chemical structures of various compounds, "hydrogen" and "-H" are interchangeable and have the same meaning unless explicitly stated otherwise.

[0033] term "(C1-C 40 "Hydrocarbyl" refers to a hydrocarbon radical having 1 to 40 carbon atoms, and the term "(C1-C 40 "Hydrocarbylene" refers to a hydrocarbon diradical having 1 to 40 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and one or more R S It is substituted or unsubstituted by. (C1-C 40 Examples of )hydrocarbil include unsubstituted or substituted (C1-C 30 )alkyl, (C3-C 30 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 10 )alkylene, (C6-C 30 )aryl or (C6-C 20 )aryl-(C1-C 10 There are alkylenes (e.g., benzyl (-CH2-C6H5)). (C1-C 40 Examples of )hydrocarbylenes include unsubstituted or substituted (C6-C 40 )arylene, ( C3-C 40 )cycloalkylene and (C1-C 40 )alkylene (e.g., (C1-C 20 There are alkylenes. Derradials may be located on the same carbon atom (e.g., -CH2-) or adjacent carbon atoms (i.e., 1,2-derradials), or may be separated by one, two, or more than two intervening carbon atoms (e.g., 1,3-derradials, 1,4-derradials, etc.). Some derradials include 1,2-derradials, 1,3-derradials, 1,4-derradials, or α,ω-derradials, while others include 1,2-derradials. α,ω-derradials are derradials that have the maximum carbon skeletal spacing between radical carbons. (C2-C20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CH2CH2-), propane-1,3-diyl (i.e., -CH2CH2CH2-), and 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-). (C6-C 40 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0034] term "(C1-C 12 )alkyl" is unsubstituted or has one or more R S It refers to a saturated linear or branched hydrocarbon radical having 1 to 12 carbon atoms substituted by. Other alkyl groups (e.g., (C x -C y )alkyl) has x to y carbon atoms and is unsubstituted or has one or more R S It is defined in a similar way to being substituted by. Unsubstituted (C1-C 12 Examples of alkyls include unsubstituted (C1-C 10 There are )alkyl; unsubstituted (C1-C6)alkyl; unsubstituted (C1-C3)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Substituted (C1-C 12 Examples of )alkyls include substituted (C1-C6)alkyls (e.g., benzyl (-CH2-C6H5)), substituted (C1-C 10 )alkyl, trifluoromethyl and [C 10 ] There are alkyl groups. The term "[C 10 ]alkyl means that the radical contains up to 10 carbon atoms including substituents, for example, one R each being a (C1-C5)alkyl S There are (C2-C5)alkyl groups substituted by. Each (C1-C5)alkyl group may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0035] term "(C3-C 30 )cycloalkyl" is unsubstituted or has one or more R S It refers to a saturated cyclic hydrocarbon radical having 3 to 30 carbon atoms substituted by. Other cycloalkyl groups (e.g., (C x -C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S It is defined in a similar way to being substituted by. Unsubstituted (C3-C 40 Examples of )cycloalkyls include unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C3-C 10 There are )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C3-C 30 Examples of )cycloalkyls include substituted (C3-C 20 )cycloalkyl, substituted (C3-C 10 There are cycloalkyl, cyclopentanone-2-yl, and 1-fluorocyclohexyl.

[0036] term "(C1-C 40 )alkylene" is unsubstituted or has one or more R S It refers to a saturated straight-chain or branched-chain diradical of 1 to 40 carbon atoms substituted by (i.e., the radical is not in the ring atom). Other alkylene groups (e.g., (C x -C y )alkylene) has x to y carbon atoms and is unsubstituted or has one or more R S It is defined in a similar way to being substituted by. Unsubstituted (C1-C 40 Examples of alkylenes include unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3), including unsubstituted (C1-C 20There is an alkylene, and here “C * " represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Substituted (C1-C 40 Examples of alkylenes include substituted (C1-C 20 )alkylene, -CF2-, -C(O)- and -(CH2) 14 There is C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosilene). As previously mentioned, there are two R S (C1-C 18 Since it can form alkylenes, substituted (C1-C 40 Examples of alkylenes also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0037] term "(C6-C 30 )aryl" is unsubstituted or (one or more R S It refers to a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical having 6 to 30 carbon atoms substituted by, wherein at least 6 to 14 of these carbon atoms are aromatic ring carbon atoms. Other aryl groups (e.g., (C x -C y )aryl) has x to y carbon atoms and is unsubstituted or has one or more R SIt is defined in a similar manner as being substituted by. Monocyclic aromatic hydrocarbon radicals contain one aromatic ring; bicyclic aromatic hydrocarbon radicals have two rings; and tricyclic aromatic hydrocarbon radicals have three rings. If a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings in the radical is aromatic. The other rings or rings of the aromatic radical may independently be fused or unfused, and may be aromatic or non-aromatic. Unsubstituted (C6-C 30 Examples of aryls include unsubstituted (C6-C 20 )aryl, unsubstituted (C6-C 18 )aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene are included. Substituted (C6-C 40 Examples of aryls include substituted (C1-C 20 )aryl; substituted (C6-C 18 )aryl; 2,4-bis([C 20 Includes ]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluorene-9-on-1-yl.

[0038] term "(C3-C 40 )cycloalkylene" is unsubstituted or has one or more R S It refers to a cyclic diradical of 3 to 40 carbon atoms substituted by (i.e., the radical is on the ring atom). Other cycloalkylene groups (e.g., (C x -C y )cycloalkylene) has x to y carbon atoms and is unsubstituted or has one or more R S It is defined in a similar way to being substituted by.

[0039] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms are O, S, S(O), and S(O). 2, Si(R C ) 2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2- or -Si(R C Includes )-, where each R C and each R P is unsubstituted (C1-C 18 )hydrocarbyl or -H, and each R N It is unsubstituted (C1-C 18 ) It is hydrocarbyl. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by heteroatoms.

[0040] term "(C1-C 40 ")heterohydrocarbyl" refers to a heterohydrocarbon radical having 1 to 40 carbon atoms, and the term "(C1-C 40 "Heterohydrocarbylene" refers to a heterohydrocarbon diradical consisting of 1 to 40 carbon atoms. (C1-C 40 )heterohydrocarbil or (C1-C 40 The heterohydrocarbon of )heterohydrocarbylene has one or more heteroatoms. The radicals of heterohydrocarbylene may be on carbon atoms or heteroatoms. The two radicals of heterohydrocarbylene may be on a single carbon atom or a single heteroatom. Additionally, of the two radicals of the diradical, one may be on a carbon atom and the other may be on a different carbon atom; one may be on a carbon atom and the other on a heteroatom; or one may be on a heteroatom and the other on a different heteroatom. Each (C1-C 40)heterohydrocarbil and (C1-C 40 )heterohydrocarbylene is unsubstituted or (one or more R S It may be aromatic or non-aromatic, saturated or unsaturated, straight or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic, substituted by) other heterohydrocarbyl groups (e.g., (C x -C y ) Heterohydrocarbyl) has x to y carbon atoms and is unsubstituted or has one or more R S It is defined in a similar way to being substituted by.

[0041] (C1-C 40 )Heterohydrocarbil can be unsubstituted or substituted. (C1-C 40 Non-limiting examples of )heterohydrocarbyl are (C1-C 40 )heteroalkyl, (C1-C 40 )hydrocarbyl-O-, (C1-C 40 )hydrocarbyl-S-, (C1-C 40 )hydrocarbil-S(O)-, (C1-C 40 )hydrocarbyl-S(O)2-, (C1-C 40 )hydrocarbyl-Si(R C )2-, (C l -C 40 )hydrocarbyl-N(R N )-, (C l -C 40 )Hydrocarbil-P(R P )-, (C2-C 40 )heterocycloalkyl, (C2-C 20 )heterocycloalkyl-(C1-C 10 )alkylene, ( C3-C 20 )cycloalkyl-(C1-C 10 )heteroalkylene, (C2-C 20 )heterocycloalkyl-(C1-C 10 )heteroalkylene, (C1-C 30 )heteroaryl, (C1-C 20 )heteroaryl-(C1-C10 )alkylene, (C6-C 20 )aryl-(C1-C 10 )heteroalkylene or (C1-C 20 )heteroaryl-(C1-C 10 It contains heteroalkylene.

[0042] term "(C3-C 30 )heteroaryl" is unsubstituted or (one or more R S It refers to a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical having a total of 3 to 50 carbon atoms and 1 to 10 heteroatoms substituted by ( ). A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical has two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. Where a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. Other rings or rings of the heteroaromatic radical may independently be non-fused or fused and aromatic or non-aromatic. Generally, other heteroaryl groups (e.g., (C x -C y )heteroaryl, e.g. (C4-C 12 A )heteroaryl) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or has one or more than one R SIt is defined in a similar manner as being substituted by. Monocyclic heteroaromatic hydrocarbon radicals are five-membered or six-membered rings. A five-membered ring has 5 - h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3; each heteroatom can be O, S, N, or P. Examples of five-membered heteroaromatic hydrocarbon radicals are pyrrole-1-yl; pyrrole-2-yl; furan-3-yl; thiophene-2-yl; pyrazole-1-yl; isoxazole-2-yl; isothiazol-5-yl; imidazole-2-yl; oxazole-4-yl; thiazole-2-yl; 1,2,4-triazole-1-yl; 1,3,4-oxadiazole-2-yl; 1,3,4-thiadiazole-2-yl; tetrazole-1-yl; Includes tetrazole-2-yl and tetrazole-5-yl. The 6-membered ring has 6 - h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridine-2-yl; pyrimidine-2-yl; and pyrazine-2-yl. Bicyclic heteroaromatic hydrocarbon radicals can be fused 5,6-ring or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals include indole-1-yl and benzimidazole-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals include quinoline-2-yl and isoquinoline-1-yl. Tricyclic heteroaromatic hydrocarbon radicals can be fused 5,6,5-rings; 5,6,6-rings; 6,5,6-rings; or 6,6,6-rings. An example of a fused 5,6,5-ring is 1,7-dihydropyrrolo[3,2-f]indole-1-yl. An example of a fused 5,6,6-ring is 1H-benzo[f]indole-1-yl. An example of a fused 6,5,6-ring is 9H-carbazole-9-yl. An example of a fused 6,6,6-ring is acryldin-9-yl.

[0043] term "(C1-C 40")heteroalkyl" refers to a saturated straight-chain or branched-chain radical containing 1 to 50 carbon atoms, or fewer carbon atoms and one or more heteroatoms. The term "(C1-C 40 ")heteroalkylene" refers to a saturated straight-chain or branched-chain diradical containing 1 to 40 carbon atoms and one or more heteroatoms. The heteroatoms of heteroalkyl or heteroalkylene are Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, SR C It may include , S(O) and S(O)2, and each heteroalkyl and heteroalkylene group is unsubstituted or one or more R S It is replaced with.

[0044] Unsubstituted (C2-C 40 Examples of )heterocycloalkyls are unsubstituted (C2-C 20 )heterocycloalkyl, unsubstituted (C2-C 10 It includes heterocycloalkyl, aziridine-1-yl, oxetane-2-yl, tetrahydrofuran-3-yl, pyrrolidine-1-yl, tetrahydrothiophene-S,S-dioxide-2-yl, morpholine-4-yl, 1,4-dioxane-2-yl, hexahydroazepine-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0045] The term "halogen atom" or "halogen" refers to the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). The term "halide" refers to fluoride (F₂), the anionic form of a halogen atom. - ), chloride (Cl - ), bromide (Br - ) or iodide(I -It means ).

[0046] The term "saturated" means the absence of carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. A saturated chemical group has one or more substituents R S When substituted by, one or more double and / or triple bonds are optionally substituent R S It may or may not be present in. The term "unsaturated" refers to containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or one or more carbon-nitrogen, carbon-phosphorus, or carbon-silicon double bonds (in heteroatom-containing groups), provided that the substituent R S This means that it does not include double bonds that may exist in or in aromatic rings that exist therein.

[0047] The terms “comprising,” “including,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, regardless of whether these terms are specifically disclosed. To avoid misunderstanding, any composition claimed through the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless otherwise stated. In contrast, the term “substantially composed of” excludes any other components, steps, or procedures from the scope of any subsequent enumeration, except those that are not essential to the functionality. The term “composed of” excludes any components, steps, or procedures that are not specifically described or enumerated.

[0048] embodiments

[0049] Process for manufacturing polyolefin elastomers

[0050] The polyolefin elastomers described herein and their desirable characteristics of high vinyl content, long chain branching, and chain-terminal unsaturation are partly attributed to the process of manufacturing the polyolefin elastomers. In one or more embodiments, the polyolefin elastomers are prepared by solution polymerizing ethylene and optionally an α-olefin comonomer in the presence of a precatalyst having the following structure (I):

[0051]

[0052] In the above formula, M is Zr or Hf, and the metal is in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is an independently selected monodentate ligand; the total catalyst is charge-neutral; and R1 and R 16 At least one of them is selected from the group consisting of structure (II), structure (III) and structure (IV):

[0053]

[0054] In structures (II), (III) and (IV), R 31-35 , R 41-48 and R 51-59 is -H, C1-C 40 Hydrocarbyl, C1-C 40 Heterohydrocarbil, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N)-, (R C )2NC(O)- or independently selected from halogen, and R C is C1-C 40 Independently selected from hydrocarbil; R 3 and R 14 C1-C independently 40 Hydrocarbyl or hydrogen; R 6 and R 11 C1-C independently 40 Hydrocarbyl or hydrogen; R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 and R 15 is C1-C 40 Hydrocarbyl, C1-C 40 Heterohydrocarbyl, ―Si(R C )3, independently selected from the group consisting of halogen atoms, hydrogen atoms, and combinations thereof; R 17 and R 18 is independently C1-C3 hydrocarbylene; R 19 and R 20 C1-C independently 40 It is hydrocarbyl or hydrogen.

[0055] In some embodiments, R 1 and R 16 Each is structure (III):

[0056]

[0057] In the above equation, R 41-48 It is independently selected from -H or C1-C6 alkyl.

[0058] In some embodiments, M is Zr.

[0059] In some embodiments, R 3 and R 14 C1-C independently 12It is an alkyl.

[0060] In some embodiments, R 6 and R 11 C1-C independently 12 It is an alkyl.

[0061] In some embodiments, R 3 , R 6 , R 11 and R 14 is independently C6-C 11 It is an alkyl.

[0062] In some embodiments, R 17 and R 18 is -CH2-.

[0063] In some embodiments, R 19 and R 20 C2-C independently 10 It is an alkyl.

[0064] In some embodiments, R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 and R 15 is a hydrogen atom.

[0065] Furthermore, polymerization can occur in the presence of a co-catalyst, and various compositions thereof are considered suitable. In one embodiment, the co-catalyst comprises alumonic acid. In a specific embodiment, the co-catalyst is modified methylalumonic acid (MMAO).

[0066] The polyolefin elastomer of the present disclosure may also be manufactured using an Al-based chain transfer agent (CTA) beta-hydride removal technique. For example, in an embodiment, the polyolefin elastomer of the present disclosure is manufactured by: 1) mixing starting materials comprising (a1) a monomer component, (b1) a chain transfer agent component, and (c1) a catalyst component comprising a precatalyst to form a solution, and polymerizing (a1) the monomer component in the solution in an amount greater than 10 mol% and less than or equal to 99 mol%; 2) heating the solution; and 3) formula A 1 L 1 Formula A by the process of the step of recovering a product comprising a polyolefin component including an unsaturated polyolefin 1 L 1 It can be prepared from an unsaturated polyolefin, and (b1) the chain transfer agent component comprises an aluminum alkyl of the formula Al(d)3, where d is independently C1 to C at each appearance. 10 It is an alkyl group; L 1 is a polyolefin; A 1 Silver vinyl group, chemical formula CH2=C(Y 1 )- vinylidene group, chemical formula Y 1 The vinylene group of CH=CH-, vinyl group and chemical formula Y 1 A mixture of vinylene groups of CH=CH-, chemical formula CH2=C(Y 1 A mixture of vinylidene groups of )-, chemical formula CH2=C(Y 1 The vinylidene group of )- and the chemical formula Y 1 A mixture of vinylene groups of CH=CH-, and vinyl groups, chemical formula CH2=C(Y 1 )-'s vinylidene group, and chemical formula Y 1 Selected from the group consisting of mixtures of CH=CH- vinylene groups; Y 1 C1 to C independently at each appearance 30It is a hydrocarbyl group. Further details regarding Al-based chain transfer agent (CTA) beta-hydride removal technology and polyolefin elastomers prepared therefrom can be found in International Publication WO 2020140067 A1, International Publication WO 2020140058 A1, and International Publication WO 2011102989 A1, each of which is incorporated herein by reference in its entirety.

[0067] In one embodiment, the precatalyst used in the process described above for producing a polyolefin elastomer using an Al-based chain transfer agent (CTA) beta-hydride removal technology may have the following structure (V):

[0068]

[0069] In one embodiment, the chain transfer agent used in the process described above for manufacturing a polyolefin elastomer using an Al-based chain transfer agent (CTA) beta-hydride removal technology may include triethylaluminum.

[0070] Various polymerization conditions are considered suitable. For example, polymerization may occur in a single reactor or multiple reactors. Various reactors, such as loop reactors or continuous stirred tank reactors (CSTRs), are considered suitable. In some embodiments, the catalyst described above enables the solution polymerization process in a single reactor. The solution polymerization process may occur at temperatures above 120°C, above 150°C, above 170°C, or above 180°C. Furthermore, the solution polymerization process may occur at pressures above 30 bar (3 MPa) or above 40 bar (4 MPa). Various hydrocarbon solvents are considered suitable during solution polymerization. In one embodiment, the solvent is an isoparaffinic solvent.

[0071] The polyolefin elastomer produced by the solution polymerization process may be an ethylene / alpha-olefin copolymer, for example, an ethylene / alpha-olefin random copolymer. The alpha-olefin comonomer is the C4-C described above. 12 It includes a comonomer. The resulting ethylene-based polymer may be a polyolefin elastomer defined above, specifically having a density of 0.860 to 0.900 g / cc; a melt index (I2) of 0.5 to 50 dg / min (wherein I2 is measured according to ASTM D1238 (190°C, 2.16 kg); and a polyolefin elastomer comprising at least 0.2 vinyls per 1,000 carbons. In some embodiments, the polyolefin elastomer has an I2 of 8.5 or higher. 10 It can have / I2, where I 10 It is measured according to ASTM D1238 (190°C, 10 kg), the percentage of vinyl in total unsaturation is 50% or more, and the oligomer level is less than 5000 ppm.

[0072] Polyolefin elastomer

[0073] An embodiment of the present disclosure relates to a rheology-modified polyolefin elastomer prepared by forming a first composition comprising 0.01% by weight to 0.3% by weight of an organic peroxide based on the combined weight of the polyolefin elastomer and the organic peroxide, and decomposing at least 75% by weight of the organic peroxide in the first composition, wherein the polyolefin elastomer has a density of 0.860 to 0.900 g / cc, at least 0.2 vinyls per 1000 carbons, and a melt index (I2) of 0.5 to 50 dg / min.

[0074] Polyolefin elastomers are polymerized reaction products of ethylene and C4-C 12It may include an ethylene-based polymer comprising an alpha-olefin comonomer. In some embodiments, the ethylene-based polymer is an ethylene / alpha-olefin random copolymer. In some embodiments, the ethylene-based polymer is a unimodal ethylene / alpha-olefin random copolymer. C4-C 12 The alpha-olefin comonomer may include various alpha-olefin comonomers, for example, 1-butene, 1-hexene, and 1-octene. In one embodiment, the alpha-olefin comonomer includes 1-octene.

[0075] The polyolefin elastomer used to form the first composition of the process described herein may have a density of 0.860 to 0.900 g / cc, 0.860 to 0.880 g / cc, or 0.865 to 0.875 g / cc.

[0076] The polyolefin elastomer used to form the first composition of the process described herein may have a melt index (I2) of 0.5 to 50 dg / min, wherein I2 is measured according to ASTM D1238 (190°C, 2.16 kg), and in further embodiments may include a melt index (I2) of 0.5 to 45 dg / min, 0.5 to 40 dg / min, 0.5 to 35 dg / min, 0.5 to 32 dg / min, or 0.5 to 30 dg / min. In some embodiments, the polyolefin elastomer may have a melt index (I2) of 0.5 or more and less than 12 dg / min, 1.0 or more and less than 12 dg / min, 2.0 or more and less than 12 dg / min, 3.0 or more and less than 12 dg / min, or 4.0 or more and less than 12 dg / min. In some embodiments, the polyolefin elastomer may have a melt index (I2) of 12 or more and less than 50 dg / min, 12 or more and less than 45 dg / min, 12 or more and less than 40 dg / min, 12 or more and less than 35 dg / min, or 12 or more and less than 30 dg / min.

[0077] In some embodiments, the melt index (I2) of the polyolefin elastomer is a range extending from a lower limit of 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, or 12.0 dg / min to an upper limit of 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, or 50 dg / min, e.g., 1.0 to 25 dg / min, 2.0 to 20 dg / min, Or it may have 3 to 18 dg / min.

[0078] Polyolefin elastomers have 8 or more I 10 It can have / I2, where I 10 I is measured according to ASTM D1238 (190°C, 10 kg), and in additional embodiments, I of 8 to 20, 8 to 15, 8 to 12, or 8 to 11, or 9 to 11, or 9.5 to 11. 10 It may include / I2. Without being limited to theory, this I 10 The / I2 range is associated with increased long-chain branching, which aids the processability of rheology-modified polyolefin elastomers prepared from these basic polyolefin elastomers.

[0079] The polyolefin elastomer may have a high degree of vinyl unsaturation proven to have 0.2 or more vinyls per 1,000 carbons, and in further embodiments may include 0.2 to 1 vinyl per 1,000 carbons, 0.2 to 0.8 vinyls per 1,000 carbons, or 0.2 to 0.6 vinyls per 1,000 carbons.

[0080] The polyolefin elastomer may include more than 0.2 unsaturated carbon atoms per 1,000 carbon atoms or more than 0.3 unsaturated carbon atoms per 1,000 carbon atoms, and in additional embodiments may include 0.35 to 2 unsaturated carbon atoms per 1,000 carbon atoms, 0.35 to 1 unsaturated carbon atoms per 1,000 carbon atoms, or 0.40 to 0.80 unsaturated carbon atoms per 1,000 carbon atoms.

[0081] Furthermore, the percentage of vinyl in the total degree of unsaturation of the polyolefin elastomer may be at least 50%, at least 55%, at least 60%, at least 65%, or at least 70%.

[0082] Additionally, the polyolefin elastomer may have an oligomer level of less than 5000 ppm, and in further embodiments may have an oligomer level of less than 4500 ppm, less than 4000 ppm, less than 3500 ppm, less than 3000 ppm, or less than 2500 ppm, less than 2000 ppm, less than 1500 ppm, less than 1000 ppm, less than 500 ppm, less than 250 ppm, or less than 200 ppm. Without being bound by theory, the polyolefin elastomer may have a high vinyl level and a low oligomer level at the chain ends due to the selection of catalyst and process conditions. In polymers with a high vinyl level and a high oligomer level, the level of oligomers having vinyl chain ends (low Mw components) may be high, and thus the crosslinking efficiency may be low.

[0083] Additionally, the polyolefin elastomer may have a number average molecular weight (Mn) of 20 to 30 kg / mol or 22 to 28 kg / mol, where Mn is measured according to conventional gel permeation chromatography (GPC). The polyolefin elastomer may have an Mw / Mn of 2.0 to 3.0, 2.4 to 3.0, or 2.5 to 2.6, where Mw (weight average molecular weight) is measured according to conventional GPC.

[0084] Furthermore, polyolefin elastomers have a rheology ratio (V) greater than 3 0.1 / V 100 It can have ), and here V 0.1 is the complex viscosity measured at 190°C at an angular frequency of 0.1 radians / sec, and V 100 is a complex viscosity measured at 190°C at an angular frequency of 100 radians / sec. In additional embodiments, the rheology ratio may be greater than 1.5, greater than 2, or greater than 4. Furthermore, the rheology of the polyolefin elastomer may be characterized by the following equation, which further considers the influence of the melt index: (V 0.1 / V 100 )* I2 0.5 When applying this equation, the polyolefin elastomer is 7.5 (dg / min) 0.5 Exceeding, 8 (dg / min) 0.5 Exceeding, 10 (dg / min) 0.5 Exceeds 14 (dg / min) 0.5 Exceeds 16 (dg / min) 0.5 Exceeding, 18 (dg / min) 0.5 Exceeding or 20 (dg / min) 0.5 It can have an excess value.

[0085] Method for manufacturing rheology-modified polyolefin elastomer

[0086] An embodiment of the present disclosure relates to a method for producing a rheology-modified polyolefin elastomer, the method comprising the steps of forming a first composition comprising 0.01 weight% to 0.3 weight% of an organic peroxide based on the combined weight of the polyolefin elastomer and the organic peroxide, and decomposing at least 75 weight% of the organic peroxide in the first composition, wherein the polyolefin elastomer has a density of 0.860 to 0.900 g / cc, at least 0.2 vinyl per 1000 carbons, and a melt index (I2) of 0.5 to 50 dg / min.

[0087] In an embodiment, at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 91 wt%, at least 92 wt%, at least 93 wt%, at least 94 wt%, at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt% of the organic peroxide in the first composition may be decomposed in the process described herein to produce a rheology-modified polyolefin elastomer.

[0088] Various organic peroxides may be used in the rheology modification processes described herein. Organic peroxides useful for rheology modification include, but are not limited to, peroxycarbonates such as, for example, tert-amylperoxy-2-ethylhexyl carbonate (TAEC); and peroxyketals such as, for example, 1,1-di(tert-amylperoxy)cyclohexane. Examples of organic peroxides include t-butylperoxyisopropyl carbonate; tert-butylperoxy-2-ethylhexyl carbonate (TBEC); tert-amylperoxy-2-ethylhexyl carbonate (TAEC); 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane (available, e.g., as Trigonox® 301 from Nouryon); tert-butylperoxyacetate; t-butylperoxybenzoate; and dicumyl peroxide. It may include 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di-(tert-butyl-peroxy)hexine-3; 1,1-di-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane; 1,1-di-(tert-butylperoxy)cyclohexane; methyl ethyl ketone peroxide; 2,5-dimethyl-hexyl-2,5-diperoxybenzoate; tert-butyl hydroperoxide; p-menthan hydroperoxide; benzoyl peroxide; p-chlorobenzoyl peroxide; tert-butylperoxyisobutyrate; hydroxyheptyl peroxide; and dicyclohexanone peroxide.

[0089] In some embodiments, the organic peroxide used for rheology modification comprises one or more of tert-butylperoxy 2-ethylhexyl carbonate (TBEC), tert-amylperoxy 2-ethylhexyl carbonate (TAEC), 1,1-di(tert-butylperoxy)cyclohexane (CH80), 1,1-di(tert-amylperoxy)cyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonan and 1,1-di-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane.

[0090] In some embodiments, the first composition comprises 0.01% to 0.3% by weight of an organic peroxide based on the combined weight of the polyolefin elastomer and the organic peroxide. In one or more embodiments, the first composition comprises, based on the combined weight of the polyolefin elastomer and the organic peroxide, 0.01 wt% to 0.3 wt% of organic peroxide, 0.01 wt% to 0.25 wt% of organic peroxide, 0.01 wt% to 0.2 wt% of organic peroxide, 0.01 wt% to 0.18 wt% of organic peroxide, 0.01 wt% to 0.16 wt% of organic peroxide, 0.01 wt% to 0.14 wt% of organic peroxide, 0.01 wt% to 0.12 wt% of organic peroxide, 0.01 wt% to 0.1 wt% of organic peroxide, 0.02 wt% to 0.3 wt% of organic peroxide, 0.02 wt% to 0.25 wt% of organic peroxide, and 0.02 wt% to 0.2 weight% of organic peroxide, 0.02 weight% to 0.18 weight% of organic peroxide, 0.02 weight% to 0.16 weight% of organic peroxide, 0.02 weight% to 0.14 weight% of organic peroxide, 0.02 weight% to 0.12 weight% of organic peroxide, 0.02 weight% to 0.1 weight% of organic peroxide, 0.03 weight% to 0.3 weight% of organic peroxide, 0.03 weight% to 0.25 weight% of organic peroxide, 0.03 weight% to 0.2 weight% of organic peroxide, 0.03 weight% to 0.18 weight% of organic peroxide, 0.03 weight% to 0.16 weight% of organic peroxide, 0.03 weight% to 0.14 weight% of organic peroxide, 0.03 weight% to 0.12 wt% organic peroxide, 0.03 wt% to 0.1 wt% organic peroxide, 0.04 wt% to 0.3 wt% organic peroxide, 0.04 wt% to 0.25 wt% organic peroxide, 0.04 wt% to 0.2 wt% organic peroxide, 0.04 wt% to 0.04 wt% to 0.18 wt% organic peroxide, 0.04 wt% to 0.16 wt% organic peroxide, 0.04 wt% to 0.14 wt% organic peroxide, 0.04 wt% to 0.12 wt% organic peroxide, 0.04 wt% to 0.1 wt% organic peroxide, 0.05 wt% to 0.3 wt% organic peroxide, 0.05 wt% to 0.25 wt% organic peroxide, 0.05 wt% to 0.2 wt% organic peroxide, 0.05 wt% to 0.18 wt% organic peroxide, 0.05 wt% to 0.16 wt% organic peroxide, 0.05 wt% to 0.14 wt% organic peroxide, 0.05 wt% to 0.12 wt% organic peroxide, or 0.05 It contains 0.1% to 0.1% by weight of organic peroxide.

[0091] In one or more embodiments, the step of forming the first composition comprises immersing an organic peroxide in a pellet comprising a polyolefin elastomer to form a peroxide-immersed polyolefin elastomer pellet. The immersion may be performed at an immersion temperature of 40°C or higher and 120°C or lower, 40°C or higher and 100°C or lower, 40°C or higher and 80°C or lower, 40°C or higher and 75°C or lower, 40°C or higher and 70°C or lower, 40°C or higher and 65°C or lower, 40°C or higher and 60°C or lower, 45°C or higher and 60°C or lower, or 45°C or higher and 55°C or lower. Immersion may be performed for an immersion period of 0.5 hours or more, e.g., 0.5 hours or more and 12 hours or less, 0.5 hours or more and 10 hours or less, 0.5 hours or more and 8 hours or less, 1 hour or more and 8 hours or less, 2 hours or more and 8 hours or less, 3 hours or more and 8 hours or less, 4 hours or more and 8 hours or less, 5 hours or more and 8 hours or less, or 5 hours or more and 7 hours or less. In some embodiments, immersion may be performed for an immersion period of 0.5 hours or more at an immersion temperature of 40°C or more and 80°C or less.

[0092] In an embodiment in which the step of forming the first composition comprises immersing an organic peroxide in a pellet, the step of decomposing at least 75 weight percent of the organic peroxide in the first composition may comprise melt blending the peroxide-immersed polyolefin elastomer pellet. Melt blending of the peroxide-immersed polyolefin elastomer pellet may be used to initiate peroxide decomposition, which may be added using other processes, such as directly heating the melt blended peroxide-immersed polyolefin elastomer pellet. In other embodiments, melt blending may be the only means of introducing heat to decompose the peroxide. In some embodiments, melt blending of the peroxide-immersed polyolefin elastomer pellet is performed for a melt blending period of at least 2x hours at a melt blending temperature equal to the x-hour half-life temperature of the organic peroxide to decompose at least 75 weight percent of the organic peroxide in the first composition.

[0093] In one or more embodiments, the step of forming the first composition may include adding the polyolefin elastomer and the organic peroxide to a continuous mixer or batch mixer in any order, and the step of decomposing at least 75 weight percent of the organic peroxide in the first composition includes melt blending the polyolefin elastomer and the organic peroxide. In some embodiments, the melt blending of the polyolefin elastomer and the organic peroxide is performed for a melt blending period of at least 2x hours at a melt blending temperature equal to the x-hour half-life temperature of the organic peroxide.

[0094] The peroxide-immersed polyolefin elastomer pellets of the first composition, or the polyolefin elastomer and organic peroxide, may be added to a batch mixer or continuous mixer for melt blending to form a melt-blended composition. The components may be added in any order, and one or more masterbatches may be prepared and added first to blend with other components. Melt blending may be performed at a temperature higher than the maximum melting temperature of the polymer in the first composition. The melt-blended composition may then be transferred to an extruder or injection molding machine, or passed through a die to form a desired article, or converted into pellets, tapes, strips, films, or some other form to prepare material for storage or to be supplied to the next molding or processing step.

[0095] Examples of mixing equipment suitable for the process described herein include internal batch mixers, such as HAAKE™, BRABENDER®, BANBURY™, or BOLLING™ internal mixers. Alternatively, continuous single-screw or twin-screw mixers, such as FARRELL™ continuous mixers, BRABENDER®, WERNER™, or PFLEIDERER™ twin-screw mixers, or BUSS™ kneading continuous extruders, may be used.

[0096] Optionally, in the method described herein, a free radical auxiliary may be used to produce a rheology-modified polyolefin elastomer during a formulation step, for example, which is discussed in more detail below. The free radical auxiliary is a monomer or low molecular weight polymer having two or more functional groups that are highly reactive with free radicals. Typically, these functional groups are methacrylates, allyls, or vinyls. The free radical auxiliary enhances the rheology modification of peroxides.

[0097] Free radical adjuvants suitable for this application include diallyl terephthalate, trialyl cyanurate (TAC), trialyl isocyanurate (TAIC), 1,2-polybutadiene, divinyl benzene, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol triacrylate, allyl methacrylate, NN′-m-phenylene bismaleimide, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (vinyl D4), methyl acrylate, butyl acrylate, methyl methylacrylate, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxy(acrylate TEMPO), and 4-allyloxy-2,2,6,6-tetramethylpiperidine-N-oxy(allyl It will include TEMPO), bis(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl) sebacate (bisTEMPO), styrene, α-methyl styrene, α-methyl styrene dimer (AMSD), 1,1-diphenylethylene (DPE), N,N,N′,N′,N″,N″-hexaallyl-1,3,5-triazine-2,4,6-triamine, toluene bismaleimide-p-quinone dioxime, nitrobenzene and diphenylguanidine.

[0098] The free radical auxiliary is appropriately present in an amount within the range of about 100 to about 10,000 parts by weight. The range is preferably about 500 to about 5,000 parts by weight, preferably 1,000 to 3,000 parts by weight.

[0099] Peroxides and free radical auxiliaries may be added by any conventional means. Exemplary procedures include immersing the polymer pellets before compounding, adding the polymer pellets while the pellets are entering a compounding device, for example, from the throat of an extruder, adding the polymer melt in a compounding device, such as a HAAKE™, BRABENDER®, BANBURY™, or BOLLING™ internal mixer, a FARRELL™ continuous mixer, or a BUSS™ kneading continuous extruder, or injecting the polymer into the extruder at the point where the extruder contents melt as 100% active ingredient (i.e., untreated) or optionally as a dispersion or solution in an oil such as processing oil.

[0100] Optionally, a second polyolefin elastomer may be used to produce a rheology-modified polyolefin elastomer in the process described herein. For example, different densities, melt indices, I 10 A second polyolefin elastomer of / I2, vinyl content, unsaturated content and / or vinyl percentage can be melt-blended with a polyolefin elastomer, peroxide, and optional free radical auxiliary.

[0101] The degree of peroxide degradation in the method described herein for producing a rheology-modified polyolefin elastomer can be determined based on the degradation kinetics of the peroxide used for rheology modification, peroxide degradation temperature(s) (e.g., melt blending temperature(s)), and peroxide degradation period(s) at said peroxide degradation temperature(s) (e.g., melt blending period(s)). For example, in an embodiment in which tert-amylperoxy 2-ethylhexyl carbonate (TAEC) is used as an organic peroxide for rheology modification having a half-life temperature of 134°C and a half-life of 0.1 hours, melt blending of a first composition containing TAEC at a melt blending temperature of at least 134°C for a melting period of at least 0.1 hours will degrade at least 50 weight% of TAEC. An additional 0.1 hour of melt blending causes at least 50 weight percent of the TAEC remaining at the end of the first hour to decompose, so that at least 75 weight percent of the original amount of TAEC is decomposed. In this example, the x-hour half-life temperature is the 0.1-hour half-life temperature, and therefore the double melt blending period will be at least 0.2 hours.

[0102] However, in the rheology-modified polyolefin elastomers described herein, the degree of peroxide degradation can be determined regardless of processing conditions, for example, by measuring the amount of residual peroxide in the rheology-modified polyolefin elastomer using capillary gas chromatography. This method can be performed using gas chromatography (GC) equipped with flame ionization detection (FID) and using an AGILENT 6890 Plus GC equipped with the AGILENT 7683 Series. AGILENT EZChrom software may be used to collect and analyze data. Residual peroxide was extracted using methylene chloride. Once residual peroxide is measured, the degree of peroxide degradation (weight%) can be calculated as 100 × [(initial peroxide (g)) - residual peroxide (g) / (initial peroxide (g))]. The measured degree of peroxide degradation may differ from the degree of peroxide degradation determined based on the blending conditions and degradation kinetics of the peroxide used in rheology modification (e.g., compared to the peroxide degradation kinetics measured and reported for a specific peroxide due to temperature variations in the blending process and different peroxide degradation kinetics of the peroxides blended into the polymer(s)), and where such a difference exists, any reference to the degree of peroxide degradation herein should be understood to refer to the lower of the two methods.

[0103] rheology-modified polyolefin elastomer

[0104] As described above, the rheology-modified polyolefin elastomer of the present disclosure may be formed by forming a first composition comprising 0.01% to 0.3% by weight of organic peroxide based on the combined weight of the polyolefin elastomer and the organic peroxide, and decomposing at least 75% by weight of the organic peroxide in the first composition, wherein the polyolefin elastomer has a density of 0.860 to 0.900 g / cc, at least 0.2 vinyl per 1000 carbons, and a melt index (I2) of 0.5 to 50 dg / min.

[0105] In an embodiment, the rheology-modified polyolefin elastomer of the present disclosure has a melt flow ratio (I) of 8 or more, e.g., 8.5 or more, 9 or more, 9.5 or more, 10 or more, 10.5 or more, 11 or more, 11.5 or more, 12 or more, 12.5 or more, 13 or more, 13.5 or more, 14 or more, 14.5 or more, 15 or more, 15.5 or more, or 16 or more. 10 / I2) may have. In some embodiments, the rheology-modified polyolefin elastomer described herein has a melt flow ratio (I) of 8 or more and 25 or less, 8.5 or more and 25 or less, 9 or more and 25 or less, 9.5 or more and 25 or less, 10 or more and 25 or less, 10.5 or more and 25 or less, 11 or more and 25 or less, 11.5 or more and 25 or less, 12 or more and 25 or less, 12.5 or more and 25 or less, 13 or more and 25 or less, 13.5 or more and 25 or less, 14 or more and 25 or less, 14.5 or more and 25 or less, 15 or more and 25 or less, 15.5 or more and 25 or less, or 16 or more and 25 or less. 10 / I2) may have. In some embodiments, the rheology-modified polyolefin elastomer described herein has a melt flow ratio (I) of 8 or more, e.g. 12.5 or more, 8 or more and 22 or less, 8.5 or more and 22 or less, 9 or more and 22 or less, 9.5 or more and 22 or less, 10 or more and 22 or less, 10.5 or more and 22 or less, 11 or more and 22 or less, 11.5 or more and 22 or less, 12 or more and 22 or less, 12.5 or more and 22 or less, 13 or more and 22 or less, 13.5 or more and 22 or less, 14 or more and 22 or less, 14.5 or more and 22 or less, 15 or more and 22 or less, 15.5 or more and 22 or less, or 16 or more and 22 or less. 10 Can have / I2).

[0106] In an embodiment, the rheology-modified polyolefin elastomer of the present disclosure has a value measured at 120°C of 2.24 or more and 100 or less, 2.24 or more and 80 or less, 2.24 or more and 75 or less, 2.24 or more and 70 or less, 2.24 or more and 60 or less, 2.24 or more and 50 or less, 2.24 or more and 40 or less, 2.24 or more and 30 or less, 2.24 or more and 20 or less, 2.24 or more and 18 or less, 2.24 or more and 16 or less, 2.24 or more and 14 or less, 2.24 or more and 12 or less, 2.24 or more and 11 or less, 4 or more and 20 or less, 4 or more and 11 or less, 4.5 or more and 20 or less, 4.5 or more and rheology ratios (V) of 12 or less, 4.5 or more and 11 or less, 2.24 or more and 5 or less, or 2.24 or more and 3 or less 0.1 / V 100 Can have ).

[0107] In an embodiment, the rheology-modified polyolefin elastomer of the present disclosure has a value measured at 120°C of 12 or more and 100 or less, 12 or more and 80 or less, 12 or more and 75 or less, 12 or more and 50 or less, 12 or more and 40 or less, 20 or more and 40 or less, 15 or more and 100 or less, 15 or more and 80 or less, 15 or more and 75 or less, 20 or more and 100 or less, 20 or more and 80 or less, 20 or more and 75 or less, 24 or more and 100 or less, 24 or more and 80 or less, 24 or more and 75 or less, 30 or more and 100 or less, 30 or more and 80 or less, 30 or more and 75 or less, 40 or more and 100 or less, 40 or more and 80 or less, 40 or more and 75 rheology ratio (V) of 50 or more and 100 or less, 50 or more and 80 or less, or 50 or more and 75 or less 0.1 / V 100 Can have ).

[0108] In some embodiments of the rheology-modified polyolefin elastomers described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is prepared by solution polymerizing ethylene and optionally an α-olefin comonomer in the presence of a precatalyst having structure (I), so that the resulting polyolefin elastomer has a melt index (I-2) of 0.5 dg / min or more and less than 12 dg / min, and the rheology-modified polyolefin elastomer has a rheology ratio (V) of 30 or more and 100 or less, e.g., 50 or more and 80 or less, measured at 120°C. 0.1 / V 100 has ).

[0109] In some embodiments of the rheology-modified polyolefin elastomers described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is prepared by solution polymerizing ethylene and optionally an α-olefin comonomer in the presence of a co-catalyst having structure (I), so that the resulting polyolefin elastomer has a melt index (I-2) of 12 dg / min or more and 50 dg / min or less, and the rheology-modified polyolefin elastomer has a rheology ratio (V) of 12 or more and 50 or less, e.g., 20 or more and 40 or less, measured at 120°C. 0.1 / V 100 has ).

[0110] In some embodiments of the rheology-modified polyolefin elastomers described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is of formula A using the Al-based chain transfer agent (CTA) beta-hydride removal technique described above. 1 L 1 The polyolefin elastomer produced by being prepared from an unsaturated polyolefin has a melt index (I-2) of 0.5 dg / min or more and less than 12 dg / min, and the rheology-modified polyolefin elastomer has a rheology ratio (V) of 4 or more and 20 or less, for example, 4.5 or more and 12 or less, measured at 120°C. 0.1 / V 100 has ).

[0111] In some embodiments of the rheology-modified polyolefin elastomers described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is of formula A using the Al-based chain transfer agent (CTA) beta-hydride removal technique described above. 1 L 1The polyolefin elastomer produced by being prepared from an unsaturated polyolefin has a melt index (I-2) of 12 dg / min or more and 50 dg / min or less, and the rheology-modified polyolefin elastomer has a rheology ratio (V) of 2.24 or more and 5 or less, for example, 2.24 or more and 3 or less, measured at 120°C. 0.1 / V 100 has ).

[0112] Method for preparing a crosslinked polyolefin elastomer formulation

[0113] The present disclosure also relates to a crosslinkable polyolefin elastomer formulation comprising a rheology-modified polyolefin elastomer and a curing package. The curing package may comprise an organic peroxide. In another embodiment, the curing package may also comprise a crosslinking aid. In yet another embodiment, the curing package may also comprise a silane coupling agent.

[0114] In one embodiment, a method for preparing a crosslinkable polyolefin elastomer formulation comprises the step of forming a second composition comprising (i) a rheology-modified polyolefin elastomer prepared using the process described herein; and (ii) a second organic peroxide comprising 0.1% to 2% by weight based on the combined weight of the rheology-modified polyolefin elastomer and the second organic peroxide. In one embodiment, the step of forming the second composition comprises immersing an additive in the rheology-modified polyolefin elastomer to form a peroxide-immersed rheology-modified polyolefin elastomer, wherein the additive comprises the second organic peroxide; optionally a crosslinking aid; and optionally a silane coupling agent.

[0115] In one or more embodiments, immersion of the additive in the rheology-modified polyolefin elastomer may be performed at an immersion temperature of 40°C or higher and 120°C or lower, 40°C or higher and 100°C or lower, 40°C or higher and 80°C or lower, 40°C or higher and 75°C or lower, 40°C or higher and 70°C or lower, 40°C or higher and 65°C or lower, 40°C or higher and 60°C or lower, 45°C or higher and 60°C or lower, or 45°C or higher and 55°C or lower. In some embodiments, immersion of the additive in the rheology-modified polyolefin elastomer may be performed for an immersion period of 0.5 hours or more, e.g., 0.5 hours or more and 12 hours or less, 0.5 hours or more and 10 hours or less, 0.5 hours or more and 8 hours or less, 1 hour or more and 8 hours or less, 2 hours or more and 8 hours or less, 3 hours or more and 8 hours or less, 4 hours or more and 8 hours or less, 5 hours or more and 8 hours or less, or 5 hours or more and 7 hours or less. In some embodiments, immersion of the additive in the rheology-modified polyolefin elastomer may be performed for an immersion period of 0.5 hours or more at an immersion temperature of 40°C or more and 80°C or less.

[0116] Various organic peroxides are considered suitable as second organic peroxides in curing packages. Peroxides useful for curing packages include, but are not limited to, peroxycarbonates such as, for example, tert-amylperoxy-2-ethylhexyl carbonate (TAEC); and peroxyketals such as, for example, 1,1-di(tert-amylperoxy)cyclohexane. Examples of organic peroxides include t-butylperoxyisopropyl carbonate; tert-butylperoxy-2-ethylhexyl carbonate (TBEC); tert-amylperoxy-2-ethylhexyl carbonate (TAEC); 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonan; tert-butylperoxyacetate; t-butylperoxybenzoate; dicumyl peroxide; and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane. It may include di-tert-butyl peroxide; 2,5-dimethyl-2,5-di-(tert-butyl-peroxy)hexine-3; 1,1-di-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane; 1,1-di-(tert-butylperoxy)cyclohexane; methyl ethyl ketone peroxide; 2,5-dimethyl-hexyl-2,5-diperoxybenzoate; tert-butyl hydroperoxide; p-menthan hydroperoxide; benzoyl peroxide; p-chlorobenzoyl peroxide; tert-butylperoxyisobutyrate; hydroxyheptyl peroxide; and dicyclohexanone peroxide. In some embodiments, the organic peroxide used in the curing package comprises one or more of tert-butylperoxy 2-ethylhexyl carbonate (TBEC), tert-amylperoxy 2-ethylhexyl carbonate (TAEC), 1,1-di(tert-butylperoxy)cyclohexane (CH80), 1,1-di(tert-amylperoxy)cyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonan, and 1,1-di-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane. In one embodiment, the organic peroxide comprises at least one of TBEC or TAEC.

[0117] Similarly, various silane coupling agents are considered suitable. For example, the silane coupling agent may comprise one or more alkoxysilane coupling agents, vinyltrimethoxysilane (VTMS), 3-(trimethoxysilyl)-propyl-methacrylate (VMMS), tetraethoxysilane (TEOS), or a combination thereof. In one or more embodiments, the silane coupling agent comprises VTMS, VMMS, or a combination thereof.

[0118] Various crosslinking aids are also considered. These are crosslinking aids, e.g., trialyl isocyanurate (TAIC), trialyl phosphate (TAP), α-methyl styrene dimer (AMSD), trialyl cyanurate (TAC), trialyl trimellitate (TATM), 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (vinyl D4), 1,1-diphenylethylene (DPE), N,N,N′,N′,N″,N″-hexaallyl-1,3,5-triazine-2,4,6-triamine, trialyl trimellitate, trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethylacrylate (TMPTMA), 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, tris(2-hydroxyethyl) It may include isocyanurate triacrylate, trivinyl cyclohexane (TVCH), or a combination thereof.

[0119] Further examples of organic peroxides, silane coupling agents and crosslinking aids are provided in International Publication WO 2023272545 A1, which is incorporated herein by reference in its entirety.

[0120] As mentioned above, the rheology-modified polyolefin elastomer of the present disclosure may allow a smaller amount of curing package to be used in a crosslinkable polyolefin elastomer formulation or a crosslinkable polyolefin elastomer prepared therefrom. For example, the curing package may be present in an amount of 0.2 to 3.0 weight% in the crosslinkable polyolefin elastomer formulation, or in other embodiments, 1.0 to 2.0 weight% or 1.5 to 2.0 weight% of the crosslinkable polyolefin elastomer formulation. Furthermore, the crosslinkable polyolefin elastomer formulation comprises 85 to 99.5 weight% of rheology-modified polyolefin elastomer, 90 to 99.5 weight% of rheology-modified polyolefin elastomer, and 98 to 99 weight% of rheology-modified polyolefin elastomer.

[0121] The organic peroxide may be present in an amount of 0.1 to 2.0 weight% in the crosslinkable polyolefin elastomer formulation, or in another embodiment, 0.2 to 1.0 weight% or 0.5 to 1.0 weight% of the crosslinkable polyolefin elastomer formulation. The silane coupling agent may be present in an amount of 0.05 to 1.0 weight% in the crosslinkable polyolefin elastomer formulation, or in another embodiment, 0.1 to 0.5 weight% or 0.1 to 0.3 weight% of the crosslinkable polyolefin elastomer formulation. The crosslinking aid may be present in an amount of 0.1 to 2.0 weight% in the crosslinkable polyolefin elastomer formulation, or in other embodiments, 0.2 to 1.0 weight% or 0.5 to 1.0 weight% of the crosslinkable polyolefin elastomer formulation.

[0122] Additional additives or fillers that may be added during polymerization, pelletization, curing, etc. may include UV absorbers and / or stabilizers, e.g., hindered amine light stabilizers, e.g., TINUVIN 770; TiO2, additional polyolefins, one or more antioxidants; processing aids, e.g., fluoropolymers, polydimethylsiloxane (PDMS), ultra-high molecular weight PDMS; ion scavengers, potential induced degradation (PID) inhibitors; other siloxanes; fumed silica, nano-Al2O3, nano-clay, and one or more other fillers. In one embodiment, the additive is present in an amount of 0.20 wt% or more, or 0.40 wt% or more, or 0.60 wt% or more, or 0.80 wt% or more, and / or 5.0 wt% or less, or 4.0 wt% or less, or 3.0 wt% or less, or 2.0 wt% or less, or 1.5 wt% or less, or 1.0 wt% or less, based on the weight of the composition.

[0123] Crosslinked polyolefin elastomer formulation

[0124] As described above, the crosslinkable polyolefin elastomer formulation of the present disclosure, prepared using the rheology modification process described herein for the chain-terminal unsaturated polyolefin elastomer described herein, achieves improved peroxide curing performance compared to crosslinkable polyolefin elastomer formulations based on polyolefin elastomers with generally low chain-terminal unsaturation and crosslinkable polyolefin elastomer formulations having chain-terminal unsaturation but without the rheology modification described herein. Accordingly, the crosslinkable polyolefin elastomer formulation of the present disclosure provides improved shear thinning rheology and an efficient peroxide curing reaction (high degree of curing and short curing time), both of which are desirable for applications such as photovoltaic (PV) encapsulant films, shoe foams, and wiring and cable compounds.

[0125] In one or more embodiments, the crosslinkable polyolefin elastomer formulation is 17.0 minutes or less, 16.8 minutes or less, 16.6 minutes or less, 16.4 minutes or less, 16.2 minutes or less, 16.0 minutes or less, 15.8 minutes or less, 15.6 minutes or less, 15.4 minutes or less, 15.2 minutes or less, 15.0 minutes, 14.8 minutes or less, 14.6 minutes or less, 14.4 minutes or less, 14.2 minutes or less, 13.0 minutes or less, 13.8 minutes or less, 13.6 minutes or less, 13.4 minutes or less, 13.2 minutes or less, 13.0 minutes or less, 12.8 minutes or less, 12.7 minutes or less, 12.6 minutes or less, 12.4 minutes or less, 12.2 minutes or less, 12.0 minutes or less, 11.8 minutes or less, It has a curing time (T90) of 11.6 minutes or less, 11.4 minutes or less, 11.2 minutes or less, 11.0 minutes or less, 10.8 minutes or less, 10.6 minutes or less, 10.4 minutes or less, 10.2 minutes or less, 10.0 minutes or less, 9.8 minutes or less, 9.6 minutes or less, 9.4 minutes or less, 9.2 minutes or less, 9.0 minutes or less, 8.8 minutes or less, 8.6 minutes or less, 8.5 minutes or less, 8.4 minutes or less, 8.2 minutes or less, 8.0 minutes or less, 7.8 minutes or less, 7.7 minutes or less, 7.6 minutes or less, 7.4 minutes or less, or even 7.2 minutes or less, where T90 is measured according to ASTM D5289 (150°C) and T90 is defined as the time required to reach 90% of the maximum torque (MH) measured during the test interval.

[0126] In some embodiments of the crosslinkable polyolefin elastomer formulations described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is prepared by solution polymerizing ethylene and optionally an α-olefin comonomer in the presence of a precatalyst having structure (I), so that the resulting polyolefin elastomer has a melt index (I-2) of 0.5 dg / min or more and less than 12 dg / min, the organic peroxide used for rheology modification has a half-life temperature of 1 hour at a maximum of 140°C, and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 7.7 minutes or less, and T90 is measured according to ASTM D5289 (150°C). In these embodiments, the second organic peroxide may be tert-amylperoxy 2-ethylhexyl carbonate (TAEC).

[0127] In some embodiments of the crosslinkable polyolefin elastomer formulations described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is prepared by solution polymerizing ethylene and optionally an α-olefin comonomer in the presence of a precatalyst having structure (I), so that the resulting polyolefin elastomer has a melt index (I-2) of 12 dg / min or more and 50 dg / min or less, and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 8.5 minutes or less, and T90 is measured according to ASTM D5289 (150°C). In these embodiments, the second organic peroxide may be tert-amylperoxy 2-ethylhexyl carbonate (TAEC).

[0128] In some embodiments of the crosslinkable polyolefin elastomer formulations described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is prepared by solution polymerizing ethylene and optionally an α-olefin comonomer in the presence of a precatalyst having structure (I), so that the resulting polyolefin elastomer has a melt index (I-2) of 0.5 dg / min or more and less than 12 dg / min, the organic peroxide used for rheology modification has a half-life temperature of 1 hour at a maximum of 140°C, and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 11.8 minutes or less, and T90 is measured according to ASTM D5289 (150°C). In these embodiments, the second organic peroxide may be tert-butylperoxy 2-ethylhexyl carbonate (TBEC).

[0129] In some embodiments of the crosslinkable polyolefin elastomer formulations described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is prepared by solution polymerizing ethylene and optionally an α-olefin comonomer in the presence of a precatalyst having structure (I), so that the resulting polyolefin elastomer has a melt index (I-2) of 12 dg / min or more and 50 dg / min or less, and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 12.7 minutes or less, and T90 is measured according to ASTM D5289 (150°C). In these embodiments, the second organic peroxide may be tert-butylperoxy 2-ethylhexyl carbonate (TBEC).

[0130] In some embodiments of the crosslinkable polyolefin elastomer formulations described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is formula A using the Al-based chain transfer agent (CTA) beta-hydride removal technique described above. 1 L 1The polyolefin elastomer produced by being prepared from an unsaturated polyolefin has a melt index (I-2) of 0.5 dg / min or more and less than 12 dg / min, and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 8.2 minutes or less, and T90 is measured according to ASTM D5289 (150°C). In this embodiment, the second organic peroxide may be tert-amylperoxy 2-ethylhexyl carbonate (TAEC).

[0131] In some embodiments of the crosslinkable polyolefin elastomer formulations described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is formula A using the Al-based chain transfer agent (CTA) beta-hydride removal technique described above. 1 L 1 The polyolefin elastomer produced by being prepared from an unsaturated polyolefin has a melt index (I-2) of 12 dg / min or more and 50 dg / min or less, and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 11.2 minutes or less, and T90 is measured according to ASTM D5289 (150°C). In this embodiment, the second organic peroxide may be tert-amylperoxy 2-ethylhexyl carbonate (TAEC).

[0132] In some embodiments of the crosslinkable polyolefin elastomer formulations described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is formula A using the Al-based chain transfer agent (CTA) beta-hydride removal technique described above. 1 L 1The polyolefin elastomer produced by being prepared from an unsaturated polyolefin has a melt index (I-2) of 0.5 dg / min or more and less than 12 dg / min, and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 12.6 minutes or less, and T90 is measured according to ASTM D5289 (150°C). In this embodiment, the second organic peroxide may be tert-butylperoxy 2-ethylhexyl carbonate (TBEC).

[0133] In some embodiments of the crosslinkable polyolefin elastomer formulations described herein, the polyolefin elastomer used to produce the rheology-modified polyolefin elastomer is formula A using the Al-based chain transfer agent (CTA) beta-hydride removal technique described above. 1 L 1 The polyolefin elastomer produced by being prepared from an unsaturated polyolefin has a melt index (I-2) of 12 dg / min or more and 50 dg / min or less, and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 16.8 minutes or less, and T90 is measured according to ASTM D5289 (150°C). In this embodiment, the second organic peroxide may be tert-butylperoxy 2-ethylhexyl carbonate (TBEC).

[0134] Cross-linked polyolefin elastomer and articles

[0135] The crosslinked polyolefin elastomer can be prepared into a crosslinkable polyolefin elastomer formulation through a curing process known to those skilled in the art. In some embodiments, curing may be initiated by heat, irradiation, electron beam radiation, or ultraviolet (UV) radiation.

[0136] Cross-linked polyolefin elastomers can be incorporated into various materials. For example, they may be included in multilayer films. Multilayer films may comprise layers of the same or different compositions. For example, the polymer used in each layer may be different, or the level of the curing component in the composition of each layer may be different. Multilayer films may comprise two or more layers, for example, two to five layers. An exemplary multilayer film is an EVA-POE-EVA three-layer film in which the polyolefin elastomer of the present invention is used in the intermediate POE layer. Additionally, as mentioned above, the article may be a capsule for a photovoltaic module.

[0137] Test method

[0138] density

[0139] Density is measured according to ASTM D792 and is gram / cm³ 3 (g / cc or g / cm²) 3 It is displayed as ).

[0140] Melt index (I 2 ) and (I 10 )

[0141] The melt index (I2) is measured according to ASTM D-1238 (190°C / 2.16 kg). Melt index (I 10 ) is measured according to ASTM D-1238 (190℃ / 10 kg).

[0142] Gel Permeation Chromatography (GPC)

[0143] The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160°C, and the column and detector compartments were set to 150°C. The columns used were four Agilent "Mixed-Type A" 30 cm 20-micron linear mixed-bed columns. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm of butylated hydroxytoluene (BHT). Nitrogen was used as the solvent source for sparging. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / min.

[0144] Calibration of the GPC column set was performed with at least 21 polystyrene standards with a narrow molecular weight distribution having molecular weights ranging from 580 to 8,400,000, said standards were arranged in six "cocktail" mixtures spaced at least 10-fold apart from individual molecular weights. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights greater than 1,000,000 and at 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards were pre-dissolved at 80°C with gentle stirring for 30 minutes and then cooled; the room temperature solution was then transferred to an autosampler dissolution oven at 160°C for 30 minutes while cooled. The molecular weight of the polystyrene standard peak was converted to the molecular weight of polyethylene using Formula 1 (as described in the literature [Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)]):

[0145] (Equation 1)

[0146] In the above formula, M is the molecular weight, A has a value of 0.4163, and B is 1.0.

[0147] Each polyethylene equivalent correction point was fitted using a fifth-order polynomial.

[0148] The total plate count of the GPC column set was performed using decane introduced into the blank sample via a micropump controlled by the PolymerChar GPC-IR system. The plate count of the chromatography system must exceed 18,000 for four Agilent "Mixed-Type A" 30 cm 20-micron linear mixed-bed columns.

[0149] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software, gravimetrically targeted to 2 mg / ml, and a solvent (containing 200 ppm BHT) was added to pre-nitrogen-sparged, septic-capped via a PolymerChar high-temperature autosampler. Samples were dissolved at 160°C for 2 hours under "low-speed" shaking.

[0150] Mn (GPC) , Mw (GPC), and Mz (GPC) The calculation was based on the GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 2 to 4, using the PolymerChar GPCOne™ software, baseline-subtracted IR chromatograms at equally spaced data acquisition points (i), and polyethylene equivalent molecular weights obtained from a narrow standard correction curve for said point (i) from Equation 1.

[0151] (Equation 2)

[0152] (Equation 3)

[0153] (Equation 4)

[0154] To monitor deviations over time, a flow marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. Using this flow marker (FM), the RV (RV) of the decane peak within each sample was (FM 샘플) ) is the RV of the Decane peak in narrow standard correction (RV (FM 보정됨) By aligning to ), the pump flow rate (flow rate) of each sample (공칭) ) was linearly corrected. Subsequently, any change in the Decane marker peak over time was used for the flow rate (flow rate) over the entire run. (유효) It is assumed to be related to the linear shift of ). After calibrating the system based on the flow marker peak, the effective flow rate (for narrow standard calibration) is calculated according to Equation 5. Processing of the flow marker peak was performed using PolymerChar GPC One™ software. An acceptable flow rate calibration is that the effective flow rate must be within + / - 0.5% of the nominal flow rate.

[0155] flux (유효) = Flow rate (공칭) * (RV (FM 보정됨) / RV (FM 샘플) ) (Equation 5)

[0156] Mobile Die Rheometer (MDR) Curing Test

[0157] Curing characteristics were measured according to ASTM D5289 using an Alpha Technologies Moving Die Rheometer (MDR) 2000 E with a 0.5° arc. For each composition, the MDR was loaded with approximately 5 g of the formulated material. For the PV encapsulant film formulation, the MDR was run at 150°C for 30 minutes. "Time versus Torque" profiles were generated over a given interval for all cases. The key parameter used to understand the degree of curing of the formulation is MH-ML (dNm), and higher MH-ML values ​​correlate with a more cross-linked polymer network. Here, MH (dNm) refers to the maximum torque applied by the MDR during the test interval; ML (dNm) refers to the minimum torque applied by the MDR during the test interval. T90 is defined as the time required to reach 90% of the maximum torque (MH) measured during the test interval.

[0158] Oligomer measurement.

[0159] Approximately 5 grams of the sample were weighed and transferred to a glass vial. 20 mL of methylene chloride was transferred to the vial using a pipette. The vial was capped with a Teflon-lined lid, and the contents were shaken at room temperature for 24 hours. After extraction, the dichloromethane (DCM) aliquot was removed and placed in a gas chromatography (GC) autosampler vial. Sample extract, DCM blank, and certified reference standard (Ultra Scientific, C 10 to C 44 , even number of hydrocarbons, n-decane, n-tetradecane, and n-tricosan (200 parts per million (ppm) and all remaining components (100 ppm in hexane)) were analyzed by GC equipped with split / non-splitting injectors and flame ionization detectors. Methylene chloride and C 44 H 90The peak areas of all peaks eluted between were determined using a chromatography data system. Peak areas for additives such as Irgafos 168, oxidized I-168, and Irganox 1076 were excluded using the settings of the chromatography data system. The parts per million of the oligomer were determined based on the total peak area of ​​the oligomer peak in the sample and the 100 ppm n-eicosan (C) in the correction standard using an external standard correction procedure. 20 H 42 It was calculated from the peak area of ​​the peak.

[0160] 1 H NMR study

[0161] The sample was prepared by adding approximately 130 mg of the sample to 3.25 g of 50 / 50 (by weight) tetrachloroethane-d2 / perchloroethylene in a NORELL 1001-7, 10 mm, NMR tube, along with 0.001 M Cr(AcAc)3 and 100 ppm of antioxidant (Irganox 168). The sample was purged to prevent oxidation by bubbling N2 through the solvent for approximately 5 minutes using a pipette inserted into the tube. Next, the tube was capped, sealed with TEFLON tape, and then immersed overnight at room temperature to promote sample dissolution. During storage, before preparation, and after preparation, the sample was kept in an N2 purging box to minimize exposure to O2. The sample was heated and vortexed at 110°C to ensure homogeneity.

[0162] 1¹H NMR was performed at a sample temperature of 120°C on a Bruker AVANCE 400 or 600 MHz spectrometer equipped with a Bruker high-temperature cryoprobe. To acquire spectra, two experiments were conducted: a control spectrum to quantify total polymer protons, and a dual pre-saturation experiment to suppress high-intensity peaks associated with polymer chains and enable a high-sensitivity spectrum for terminal group quantification. The control was run with a ZG pulse, TD 16384, NS 16, DS 4, SWH 10,000 Hz, AQ 1.64 s, and D114 s. The dual pre-saturation experiment was performed with a modified pulse sequence, lc1prf2.zz, TD 16384, NS 64 scans, DS 4, SWH 10,000 Hz, AQ 1.64 s, D11 s, and D114 s. 13 The experiment was performed for 13 seconds. Unsaturation measurements were made according to the method described below. The area under resonance of the polymer chains (i.e., CH, CH2, and CH3 within the polymer) was measured from the spectrum obtained during the first experiment described above (control spectrum). The area under four major types of unsaturation (i.e., vinyl, vinylene, trisubstituted, and vinylidene) was measured from the spectrum obtained during the second (pre-saturation) experiment described above. Both spectra were normalized to the area under resonance in the solvent. The moles of each unsaturation were calculated by dividing the area under the unsaturation resonance by the number of protons contributing to that resonance. The moles of carbon within the polymer were calculated by dividing the area under the peak for the polymer chains (i.e., CH, CH2, and CH3 within the polymer) by 2. Subsequently, the total amount of unsaturation was expressed as the relative ratio of the total moles of unsaturation to the moles of carbon within the polymer, expressed as the number of unsaturations per 1,000 carbons.

[0163] Dynamic Mechanical Spectroscopy (DMS).

[0164] The rheology of the elastomers was analyzed by DMS using an Advanced Rheometric Expansion System (ARES) equipped with a 25 mm stainless steel parallel plate. Unless otherwise specified, constant temperature dynamic frequency sweeps ranging from 0.1 to 100 rad / s were performed at 190°C under nitrogen. Samples approximately 25.4 mm in diameter were cut from compression-molded parts. The samples were placed on a bottom plate and melted for 5 minutes. Subsequently, the plate was closed with a 2.0 mm gap, and the samples were cut to a diameter of 25 mm. Before starting the test, for the elastomers, the samples were equilibrated at 120°C or 190°C for 5 minutes. Complex viscosity was measured at a constant strain amplitude of 5% when testing at 120°C or 10% when testing at 190°C. The complex viscosity measured at 0.1 rad / s was V 0.1 Report as, and the complex viscosity measured at 100 rad / s is V 100 Reports as. Designated V 0.1 , V 100 or V 0.1 / V 100 The test temperature corresponding to the ratio (i.e., 120°C or 190°C) will be specified herein when these characteristics are referenced.

[0165] Examples

[0166] Polyolefin elastomer

[0167] The polyolefin elastomers used in the examples are provided in Tables 1A and 1B below.

[0168] [Table 1A]

[0169]

[0170] [Table 1B]

[0171]

[0172] Manufacture of polyolefin elastomers

[0173] The polyolefin elastomers of Tables 1A and 1B were prepared in a fully mixed hydraulically charged polymerization reactor operated under steady-state conditions. All raw materials (ethylene monomer and 1-octene comonomer) and process solvent (high-purity isoparaffinic solvent with a narrow boiling range, Isopar-E supplied by ExxonMobil Chemical Company) were purified by molecular sieve before being introduced into the reaction environment. Hydrogen was supplied pressurized to a high-purity grade and was not further purified. The ethylene flow rate and reactor volume were selected to obtain the residence times specified in Table 2A. The catalyst, co-catalyst, and chain transfer agent used are listed in Table 3. The solvent, comonomer, hydrogen, catalyst, co-catalyst, and chain transfer agent (for POE K and POE J prepared using the beta-hydride removal technique described above) were supplied to the reactor according to the process conditions listed in Tables 2A and 2B. The catalyst flow rate was adjusted to achieve the desired ethylene conversion rate. The reactor temperature was measured at or near the reactor outlet. For POE J and POE K, the reactor effluent was heated to 240°C by passing it through a post-reactor heater (PRH), where the removal of beta-H from polymeryl-Al occurred. A small amount of water or isopropyl alcohol, along with any stabilizer or other additive, was added after the PRH and before devolatilization. Subsequently, the reactor effluent was introduced into a devolatilization system where the polymer was removed from the apolymer stream. The copolymer was separated and pelletized.

[0174] [Table 2A]

[0175]

[0176] [Table 2B]

[0177]

[0178] [Table 3]

[0179]

[0180] The BPP-A catalyst was prepared according to the following 3-step process:

[0181] Step 1: Synthesis of Subfragment 3

[0182]

[0183] This reaction was performed in a nitrogen-filled glove box. In DMF (7 mL) 1 (5.52 g, 19.3 mmol), 2 A slurry of (International Publication WO 2022015369 A1) (1.65 g, 7.74 mmol) and K3PO4 (5.75 g, 27.1 mmol) was heated to 75°C and maintained at this temperature for 5 hours while stirring. After this time, the temperature was lowered to 70°C and maintained at this temperature for 11 hours while stirring. After cooling to room temperature, the mixture was removed from a glove box. Et2O (10 mL) was added to the reaction vial, and the mixture was filtered through a 1:1 (40 g) basic alumina / SiO2 gel plug. The plug was further extracted with Et2O (3 x 30 mL). The combined Et2O extracts were transferred to a separatory funnel and washed with 4 N NaOH (10 mL), H2O (10 mL), brine (10 mL), 4 N NaOH (10 mL), H2O (10 mL), and brine (10 mL). Subsequently, the Et2O layer was dried over Na2SO4 and filtered through a 250 mL RB flask to remove the Na2SO4. The Et2O was removed by rotary evaporator. 3 (5.25 g, 7.39 mmol, yield: 96%) was obtained as a colorless oil, which was used without further purification. 1H NMR (400 MHz, chloroform-d) δ 7.49 (d, J = 2.4 Hz, 2H), 7.24 (dd, J = 8.6, 2.4 Hz, 2H), 6.96 (d, J = 8.7 Hz, 2H), 3.94 (s, 4H), 1.69 (s, 4H), 1.40 - 1.36 (m, 2H), 1.32 (s, 12H), 1.21 (app d, J = 7.4 Hz, 12H), 0.74 (s, 18H).

[0184] Synthesis of 5 (compound 4 (It was manufactured as described in International Publication WO 2018170138)

[0185]

[0186] Degassed THF (5 mL) and degassed water (2 mL) 4 (0.948 g, 1.63 mmol), 3It was added to a 40 mL vial filled with (0.330 g, 0.464 mmol), PdCl(crotyl)Amphos (0.00861 g, 0.0186 mmol), and NaOH (0.0929 g, 2.32 mmol). The reaction was heated to 50°C and maintained at this temperature for 16 hours. Afterward, the reaction was cooled to room temperature. Et2O (20 mL) and saturated aqueous NH4Cl (10 mL) were added to the reaction mixture. After shaking the solution, the layers separated, the organic phase was removed using a pipette, and transferred to a 4 oz bottle containing Na2SO4. The aqueous phase was further extracted with Et2O (20 mL). The combined Et2O extract was filtered through a round-bottom flask to remove Na2SO4 and concentrated until dry. After adding THF (10 mL) and MeOH (10 mL) to the separated material, high-concentration HCl (5 drops from a glass pipette) was added. The solution was heated to 85°C (ambient temperature), stirred for 18 hours, and then the solvent was removed under reduced pressure. The yellow oil was treated with isopropyl alcohol (IPA) (10 mL) via rotary evaporator, the oil was taken in IPA (15 mL), placed in a rotary evaporator bath, and heated to 55°C while rotating. The solution was then removed from the bath and rotated at room temperature, eventually precipitating a solid. After 1 hour at room temperature, the solid was collected by filtration. The solid was washed with IPA (2 x 3 mL). IPA / MeOH (1:1, 15 mL) was added to the solid (approx. 420 mg) in a 100 mL RB flask, and the flask was placed in a rotary evaporator bath and heated to 75°C while rotating. The suspension (not completely soluble) was subsequently removed from the bath and spun at room temperature. After 1 hour at room temperature, the solid was subsequently collected by filtration. The solid was washed with IPA (2 x 3 mL).MeOH / Et2O (5:1, 18 mL) was added to the solid (approx. 360 mg) in a 100 mL RB flask, and the flask was placed in a rotary evaporator bath and heated to 45°C while rotating. The suspension (not completely soluble) was subsequently removed from the bath and kept at room temperature. After leaving it at room temperature overnight, the solid was collected by filtration. The solid was washed with MeOH (2 x 3 mL). 5 (0.290 g, 0.211 mmol, yield: 45%) was obtained as a white solid. 1 H NMR (400 MHz, chloroform-d) δ 8.23 ​​(d, J = 7.6 Hz, 4H), 7.39 - 7.26 (m, 10H), 7.22 - 7.15 (m, 4H), 7.12 (d, J = 2.4 Hz, 4H), 6.66 (s, 2H), 5.76 (br s, J = 21.5 Hz, 2H), 5.53 (s, 2H), 3.42 (br s, 4H), 1.65 (s, 4H), 1.59 - 1.51 (m, 4H), 1.32 - 1.06 (m, 51H), 0.85 (t, J = 6.8 Hz, 6H), 0.79 - 0.65 (m, 32H).

[0187] Step 3: Synthesis of BPP-A

[0188]

[0189] MeMgBr (3 M in diethyl ether, 0.283 mL, 0.849 mmol) in tetrachlorozirconium (0.0475 g, 0.204 mmol) and in Et2O (10 mL) and toluene (2 mL) 5It was added to a room temperature suspension of (0.275 g, 0.200 mmol). After stirring the mixture for 4 hours, additional MeMgBr (50 μL) was added, and the reaction mixture was then stirred overnight at room temperature. After this time, the solvent was removed under reduced pressure. Pentane (10 mL) was added to the dark residue and passed through a CELITE pad. The residue and pad were extracted with additional pentane (10 mL). The combined pentane extract was concentrated until dry to obtain BPP-A (0.255 g, 0.171 mmol, tndbf: 85%). 1 H NMR (400 MHz, benzene-d6) δ 8.37 (d, J = 7.7 Hz, 2H), 8.10 (dd, J = 7.2, 1.7 Hz, 2H), 7.66 (d, J = 8.1 Hz, 2H), 7.59 (d, J = 2.5 Hz, 2H), 7.55 (d, J = 2.5 Hz, 2H), 7.52 (d, J = 2.5 Hz, 2H), 7.51 - 7.44 (m, 2H), 7.43 - 7.34 (m, 4H), 7.12 (dd, J = 7.8, 1.6 Hz, 3H), 7.05 (dd, J = 5.5, 3.3 Hz, 2H), 5.17 (d, J = 8.7 Hz, 2H), 4.24 (d, J = 14.0 Hz, 2H), 3.24 (d, J = 14.0 Hz, 2H), 1.88 (d, J = 14.6 Hz, 2H), 1.60 (d, J = 14.6 Hz, 3H), 1.45 - 1.21 (m, 50H), 1.19 (s, 6H), 0.80 (s, 18H), 0.57 (t, J = 7.9 Hz, 12H), 0.37 (p, J = 7.4 Hz, 2H), -0.88 (s, 6H).

[0190] Without being limited by theory, BPP-A was found to result in high vinyl levels at the chain-terminals along with a low oligomer content in the polymer.

[0191] Preparation of rheology-modified polyolefin elastomers

[0192] Table 4 below shows the decomposition kinetics in terms of the organic peroxide used in the examples and half-life temperatures of 0.1 hours, 1 hour, and 10 hours.

[0193] The rheology-modified polyolefin elastomers of Table 5 were prepared by reactive formulation using a BRABENDER® Twin-Screw Extruder DSE-20 with a screw diameter of 20 mm, a screw flight depth of 3.75 mm, a screw length of 800 mm, and idle speed. First, the pellets were immersed in fluoride HDPE with peroxide in an oven at 50°C for 6 hours. Subsequently, the peroxide-immersed polyolefin elastomer pellets were fed into a twin-screw extruder for reactive extrusion at 100 revolutions per minute (rpm), for example, at 210°C when the modified peroxide was Trigonox 301 and at 160°C when the modified peroxide was TAEC or TBEC. The rheology-modified polyolefin elastomers were prepared as I2 and I 10 Melt index and complex viscosity V measured at 120°C 0.1 and V 100 Polyolefin elastomers used to produce IE-1 to IE-6 (LCB-11, LCB-12, LCB-15, LCB-16, LCB-19, and LCB-20) were prepared by solution polymerizing ethylene and 1-octene comonomers in the presence of a precatalyst having a structure according to structure (I), particularly BPP-A.

[0194] The rheology-modified polyolefin elastomers of Table 6 were prepared by reactive formulation using a BRABENDER® Internal Mixer 50EHT equipped with a roller rotor. First, the polyolefin elastomer was placed in the bowl of the mixer and melted by mixing at 20 rpm for 5 minutes at 200°C when the modifying peroxide was Trigonox 301 and at 140°C when the modifying peroxide was CH80. Subsequently, the peroxide was supplied, and mixing was continued at the same temperature at 50 rpm for 10 minutes. Polyolefin elastomers used to prepare IE-7 to IE-14 (LCB-1 to LCB-8) were prepared by solution polymerization of ethylene and 1-octene comonomers in the presence of a Cat 14 precatalyst.

[0195] [Table 4]

[0196]

[0197] [Table 5]

[0198]

[0199] As can be seen in Table 5 above, the trigonox-modified chain-terminated unsaturated polyolefin elastomers POE A (I2 = 5.1 dg / min) and POE B (I2 = 12.8 dg / min), IE-1 and IE-2 respectively, had a melt flow ratio (I2) measured at 120°C that was higher than that of the conventional trigonox-modified polyolefin elastomers PV8669 (I2 = 4.9 dg / min) and PV8660 (I2 = 13.3 dg / min), CE-2 and CE-1 respectively. 10 / I2) and rheology ratio (V 0.1 / V 100 ) was higher. Similarly, TAEC-modified chain-terminated unsaturated polyolefin elastomers POE A and POE B, which are IE-3 and IE-4, had a melt flow ratio (I) measured at 120°C higher than that of conventional TAEC-modified polyolefin elastomers POE H (PV8669) and POE I (PV8660), which are CE-4 and CE-3, respectively.10 / I2) and rheology ratio (V 0.1 / V 100 ) was higher. Similarly, TBEC-modified chain-terminated unsaturated polyolefin elastomers POE A and POE B, which are IE-5 and IE-6, had a melt flow ratio (I) measured at 120°C higher than that of conventional TBEC-modified polyolefin elastomers POE H (PV8669) and POE I (PV8660), which are CE-6 and CE-5, respectively. 10 / I2) and rheology ratio (V 0.1 / V 100 ) was higher.

[0200] [Table 6]

[0201]

[0202] As can be seen in Table 6 above, the Trigonox-modified chain-terminal unsaturated polyolefin elastomers of POE J as IE-7 and IE-9 (I2 = 10.6 dg / min), and the CH80-modified chain-terminal unsaturated polyolefin elastomers of POE J as IE-11 and IE-13, had a rheology ratio (V) measured at 120°C compared to the chain-terminal unsaturated polyolefin elastomer POE J as CE-7 that was not treated with rheology modification. 0.1 / V 100 ) was higher. Similarly, the Trigonox-modified chain-terminal unsaturated polyolefin elastomers of POE K (IE-8 and IE-10) (I2 = 30.1 dg / min), and the CH80-modified chain-terminal unsaturated polyolefin elastomers of POE K (IE-12 and IE-14) had a rheology ratio (V) measured at 120°C higher than that of the CE-8 untreated chain-terminal unsaturated polyolefin elastomer POE J. 0.1 / V 100 ) was higher.

[0203] Preparation of crosslinked polyolefin elastomers

[0204] The crosslinkable polyolefin formulation of Table 7A was prepared by forming crosslinkable polyolefin elastomer pellets by immersing polymer pellets prepared from POE H (PV8669), POE I (PV8660), POE A, POE B, and the rheology-modified examples (LCB-9 to LCB-20) of Table 5 in TAEC in a fluoride HDPE bottle at 50°C for 6 hours. The crosslinkable polyolefin formulation of Table 7B was prepared by forming crosslinkable polyolefin elastomer pellets by immersing polymer pellets prepared from POE H (PV8669), POE I (PV8660), POE A, POE B, and the rheology-modified examples (LCB-9 to LCB-20) of Table 5 in TBEC in a fluoride HDPE bottle at 50°C for 6 hours. Table 8 includes selected examples of Table 7A along with two additional comparative examples of crosslinkable polyolefin formulations corresponding to the conventional polyolefin elastomer POE H (PV8669) and the chain-terminated unsaturated polyolefin elastomer POE B, respectively, with an increased loading of 1.1 wt% peroxide. The crosslinkable polyolefin formulation of Table 9 was prepared by compression molding a 1 mm thick plaque at 120°C and 10 megapascals (MPa) for 5 minutes, cutting it into 3 mm x 3 mm samples, and immersing them in organic peroxide(s) at 50°C for 6 hours. Curing characteristics for the crosslinkable polyolefin formulations of Tables 7A, 7B, 8, and 9 were measured using a movable dirheometer according to ASTM D5289.

[0205] [Table 7A]

[0206]

[0207] [Table 7B]

[0208]

[0209] [Table 8]

[0210]

[0211] [Table 9]

[0212]

[0213] As can be seen in Tables 7A through 9 above, crosslinkable polyolefin formulations prepared from rheology-modified polyolefin elastomers of the present disclosure exhibit shorter curing times (T90) than crosslinkable polyolefin formulations prepared from rheology-modified commercial polyolefin elastomers as well as from chain-terminal unsaturated polyolefin elastomers that are not treated with rheology modification. For example, it can be seen from Table 8 that CE-29 and CE-30, corresponding to the conventional polyolefin elastomer POE H (PV8669) and chain-terminal unsaturated polyolefin elastomer POE B, respectively, having an increased TAEC loading of 1.1 wt%, have longer curing times than IE-18, corresponding to the TAEC-modified chain-terminal unsaturated polyolefin elastomer POE B, having a TAEC loading of 1.0 wt%. This comparison demonstrates that, for similar melt index base resins, the rheology modification process described herein improves curing performance compared to crosslinked polyolefin formulations prepared from not only chain-terminal unsaturated polyolefin elastomers not treated with rheology modification, but also commercially available rheology-modified polyolefin elastomers.

[0214] According to a first aspect of the present disclosure, a method for producing a rheology-modified polyolefin elastomer comprises the steps of forming a first composition comprising 0.01% by weight to 0.3% by weight of an organic peroxide based on the combined weight of the polyolefin elastomer and the organic peroxide, and decomposing at least 75% by weight of the organic peroxide in the first composition, wherein the polyolefin elastomer has a density of 0.860 to 0.900 g / cc, at least 0.2 vinyl per 1000 carbons, and a melt index (I2) of 0.5 to 50 dg / min.

[0215] The second embodiment includes the first embodiment, wherein the rheology-modified polyolefin elastomer has an I of 8.5 or higher 10 With / I2, I 10 This is measured according to ASTM D1238 (190℃, 10 kg).

[0216] The third embodiment comprises the first embodiment, wherein the rheology-modified polyolefin elastomer has an I of 12.5 or more 10 With / I2, I 10 This is measured according to ASTM D1238 (190℃, 10 kg).

[0217] The fourth embodiment comprises any one of the first to third embodiments, and the polyolefin elastomer has at least 0.3 unsaturations per 1,000 carbon atoms.

[0218] The fifth embodiment comprises any one of the first to fourth embodiments, and the polyolefin elastomer has a percentage of vinyl at a total degree of unsaturation of 50% or more.

[0219] The sixth embodiment comprises any one of the first to fifth embodiments, and the polyolefin elastomer has an oligomer level of less than 5000 ppm.

[0220] The seventh embodiment comprises any one of the first to sixth embodiments, and the first composition comprises 0.03 weight% to 0.2 weight% of an organic peroxide based on the combined weight of the polyolefin elastomer and the organic peroxide.

[0221] The eighth embodiment comprises any one of the first to seventh embodiments, and the organic peroxide comprises one or more of tert-butylperoxy 2-ethylhexyl carbonate (TBEC), tert-amylperoxy 2-ethylhexyl carbonate (TAEC), 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonan and 1,1-di-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane.

[0222] The ninth embodiment includes any one of the first to eighth embodiments, and the melt index (I2) of the polyolefin elastomer is 0.5 to 35 dg / min.

[0223] The 10th embodiment comprises any one of the 1st to 9th embodiments, and the step of forming the 1st composition comprises immersing an organic peroxide in a pellet comprising a polyolefin elastomer to form a peroxide-immersed polyolefin elastomer pellet.

[0224] The 11th embodiment includes any one of the 1st to 10th embodiments, and the immersion is performed at an immersion temperature of 80°C or lower for an immersion period of 0.5 hours or more.

[0225] The 12th embodiment comprises either the 10th or 11th embodiment, and the step of decomposing at least 75 weight percent of the organic peroxide in the 1st composition comprises melt blending the peroxide-immersed polyolefin elastomer pellets.

[0226] The 13th embodiment includes the 12th embodiment, and the melt blending of the peroxide-immersed polyolefin elastomer pellets is performed for a melt blending period of 2x hours or more at a melt blending temperature equal to the x-hour half-life temperature of the organic peroxide.

[0227] The 14th embodiment includes either the 12th or 13th embodiment, and melt blending is performed using a continuous mixer or a batch mixer.

[0228] The 15th embodiment comprises any one of the 1st to 9th embodiments, wherein the step of forming the first composition comprises adding a polyolefin elastomer and an organic peroxide to a continuous mixer or a batch mixer, and the step of decomposing at least 75 weight percent of the organic peroxide in the first composition comprises melt blending the polyolefin elastomer and the organic peroxide.

[0229] The 16th embodiment comprises any one of the 1st to 9th embodiments or the 15th embodiment, and the melt blending of the polyolefin elastomer and the organic peroxide is performed for a melt blending period of 2x hours or more at a melt blending temperature equal to the x-hour half-life temperature of the organic peroxide.

[0230] The 17th embodiment comprises any one of the 1st to 16th embodiments, wherein the polyolefin elastomer is prepared by solution polymerizing ethylene and optionally an α-olefin comonomer in the presence of a precatalyst having the structure (I) below, and

[0231]

[0232] In the above formula, M is Zr or Hf, and the metal is in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is an independently selected monodentate ligand; the total catalyst is charge-neutral; and R 1 and R 16 At least one of them is selected from the group consisting of structure (II), structure (III) and structure (IV):

[0233]

[0234] In the above equation, R 31-35 , R 41-48 , and R 51-59 is independently -H, (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R CC(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or selected from halogen, and R C is independently (C1-C 40 Selected from )hydrocarbil; R 3 and R 14 C1-C independently 40 Hydrocarbyl or hydrogen; R 6 and R 11 C1-C independently 40 Hydrocarbyl or hydrogen; R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 and R 15 is C1-C 40 Hydrocarbyl, C1-C 40 Heterohydrocarbyl, ―Si(R C )3, independently selected from the group consisting of halogen atoms, hydrogen atoms, and combinations thereof; R 17 and R 18 is independently C1-C3 hydrocarbylene; R 19 and R 20 C1-C independently 40 It is hydrocarbyl or hydrogen.

[0235] The 18th mode includes the 17th mode, and R 1 and R 16 These are each structures (III),

[0236]

[0237] In the above equation, R 41-48 It is independently selected from -H or C1-C6 alkyl.

[0238] The 19th embodiment includes either the 17th or 18th embodiment, and R3 and R 14 C1-C independently 12 It is an alkyl.

[0239] The 20th embodiment includes any one of the 17th to 19th embodiments, and R 6 and R 11 This independently C1-C 12 It is an alkyl.

[0240] The 21st embodiment includes any one of the 17th to 20th embodiments, and R 3 , R 6 , R 11 and R 14 C6-C independently 11 It is an alkyl.

[0241] The 22nd embodiment includes any one of the 17th to 21st embodiments, and R 17 and R 18 This is -CH2-.

[0242] The 23rd embodiment includes any one of the 17th to 22nd embodiments, and R 19 and R 20 This independently C2-C 10 It is an alkyl.

[0243] The 24th embodiment includes any one of the 17th to 23rd embodiments, and R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 and R 15 is a hydrogen atom.

[0244] The 25th embodiment includes any one of the 17th to 24th embodiments, and the pre-catalyst is halogen-free.

[0245] The 26th embodiment comprises any one of the 17th to 25th embodiments, and polymerization occurs in a reactor at a temperature greater than 150°C.

[0246] The 27th embodiment comprises any one of the 17th to 26th embodiments, and polymerization occurs in the presence of a co-catalyst comprising alumonic acid.

[0247] The 28th embodiment includes any one of the 17th to 27th embodiments, and M is Zr.

[0248] The 29th embodiment comprises any one of the 17th to 28th embodiments, and the polyolefin elastomer is an ethylene / alpha-olefin copolymer.

[0249] The 30th embodiment comprises any one of the 17th to 29th embodiments, wherein the melt index (I2) of the polyolefin elastomer is 0.5 dg / min or more and less than 12 dg / min; and the rheology-modified polyolefin elastomer has a rheology ratio (V) of 30 or more and 100 or less. 0.1 / V 100 With ), here V 0.1 is the complex viscosity of the rheology-modified polyolefin elastomer measured at 120°C at 0.1 radians / sec; V 100 is the complex viscosity of a rheology-modified polyolefin elastomer measured at 120°C at 100 radians / sec.

[0250] The 31st embodiment includes the 30th embodiment, and the rheology ratio (V) of the rheology-modified polyolefin elastomer 0.1 / V 100 ) is 50 or more and 80 or less.

[0251] The 32nd embodiment comprises any one of the 17th to 29th embodiments, wherein the melt index (I2) of the polyolefin elastomer is 12 dg / min or more and 50 dg / min or less; and the rheology-modified polyolefin elastomer has a rheology ratio (V) of 12 or more and 50 or less. 0.1 / V 100 With ), here V 0.1 is the complex viscosity of the rheology-modified polyolefin elastomer measured at 120°C at 0.1 radians / sec; V 100is the complex viscosity of a rheology-modified polyolefin elastomer measured at 120°C at 100 radians / sec.

[0252] The 33rd embodiment includes the 32nd embodiment, and the rheology ratio (V) of the rheology-modified polyolefin elastomer 0.1 / V 100 ) is 20 or more and 40 or less.

[0253] The 34th embodiment comprises any one of the 17th to 29th embodiments, the 30th embodiment, or the 31st embodiment, wherein the melt index (I2) of the polyolefin elastomer is 0.5 dg / min or more and less than 12 dg / min; and the rheology-modified polyolefin elastomer has an I2 of 14 or more and 25 or less. 10 With / I2, here I 10 It is measured according to ASTM D1238 (190℃, 10 kg).

[0254] The 35th embodiment includes the 34th embodiment, and I of a rheology-modified polyolefin elastomer 10 / I2 is 16 or more and 22 or less.

[0255] The 36th embodiment comprises any one of the 17th to 29th embodiments, the 32nd embodiment, or the 33rd embodiment, wherein the melt index (I2) of the polyolefin elastomer is 12 dg / min or more and 50 dg / min or less; and the rheology-modified polyolefin elastomer has an I of 10.0 or more and 25 or less. 10 With / I2, here I 10 It is measured according to ASTM D1238 (190℃, 10 kg).

[0256] The 37th embodiment includes the 36th embodiment, and I of a rheology-modified polyolefin elastomer 10 / I2 is 12.5 or greater and 22 or less.

[0257] The 38th embodiment comprises any one of the 1st to 16th embodiments, wherein the polyolefin elastomer is of formula A 1 L 1The method is prepared from an unsaturated polyolefin, and comprises: 1) a step of forming a solution by mixing starting materials comprising (a1) a monomer component, (b1) a chain transfer agent component, and (c1) a catalyst component including a precatalyst, and polymerizing more than 10 mol% to 99 mol% of the (a1) monomer component in the solution; 2) a step of heating the solution; and 3) formula A 1 L 1 The method comprises the step of recovering a product comprising a polyolefin component including an unsaturated polyolefin, wherein (b1) the chain transfer agent component comprises an aluminum alkyl of the formula Al(d)3, and d is independently C1 to C at each appearance 10 It is an alkyl group; L 1 is a polyolefin; A 1 Silver vinyl group, chemical formula CH2=C(Y 1 )- vinylidene group, chemical formula Y 1 The vinylene group of CH=CH-, vinyl group and chemical formula Y 1 A mixture of vinylene groups of CH=CH-, chemical formula CH2=C(Y 1 A mixture of vinylidene groups of )-, chemical formula CH2=C(Y 1 The vinylidene group of )- and the chemical formula Y 1 A mixture of vinylene groups of CH=CH-, and vinyl groups, chemical formula CH2=C(Y 1 )-'s vinylidene group, and chemical formula Y 1 Selected from the group consisting of mixtures of CH=CH- vinylene groups; Y 1 C1 to C independently at each appearance 30 It is a hydrocarbyl group.

[0258] The 39th embodiment includes the 38th embodiment, and the precatalyst has the following structure (V):

[0259]

[0260] The 40th embodiment comprises either the 38th or 39th embodiment, and the chain transfer agent comprises triethylaluminum.

[0261] The 41st embodiment comprises any one of the 38th to 40th embodiments, and the polyolefin elastomer is an ethylene / alpha-olefin copolymer.

[0262] The 42nd embodiment comprises any one of the 38th to 41st embodiments, wherein the melt index (I2) of the polyolefin elastomer is 0.5 dg / min or more and less than 12 dg / min; and the rheology-modified polyolefin elastomer has a rheology ratio (V) of 4 or more and 20 or less. 0.1 / V 100 With ), here V 0.1 is the complex viscosity of the rheology-modified polyolefin elastomer measured at 120°C at 0.1 radians / sec; V 100 is the complex viscosity of a rheology-modified polyolefin elastomer measured at 120°C at 100 radians / sec.

[0263] The 43rd embodiment includes the 42nd embodiment, and the rheology ratio (V) of the rheology-modified polyolefin elastomer 0.1 / V 100 ) is 4.5 or higher and 12 or lower.

[0264] The 44th embodiment comprises any one of the 38th to 41st embodiments, wherein the melt index (I2) of the polyolefin elastomer is 12 dg / min or more and 50 dg / min or less; and the rheology-modified polyolefin elastomer has a rheology ratio (V) of 2.24 or more and 5 or less. 0.1 / V 100 With ), here V 0.1 is the complex viscosity of the rheology-modified polyolefin elastomer measured at 120°C at 0.1 radians / sec; V 100 is the complex viscosity of a rheology-modified polyolefin elastomer measured at 120°C at 100 radians / sec.

[0265] The 45th embodiment includes the 44th embodiment, and the rheology ratio (V) of the rheology-modified polyolefin elastomer 0.1 / V 100 ) is 2.24 or higher and 3.0 or lower.

[0266] The 46th embodiment includes any one of the 1st to 29th embodiments, and the melt index (I2) of the polyolefin elastomer is 0.5 dg / min or more and less than 12 dg / min.

[0267] The 47th embodiment includes any one of the 1st to 29th embodiments, and the melt index (I2) of the polyolefin elastomer is 12 dg / min or more and 50 dg / min or less.

[0268] The 48th aspect of the present disclosure comprises a rheology-modified polyolefin elastomer prepared using any one of the methods of the 1st to 47th aspects.

[0269] According to the 49th aspect of the present disclosure, a rheology-modified polyolefin elastomer comprises a reaction product of a polyolefin elastomer and an organic peroxide, wherein the polyolefin elastomer has a density of 0.860 to 0.900 g / cc; a melt index (I2) of 0.5 to 50 dg / min (wherein I2 is measured according to ASTM D1238 (190°C, 2.16 kg)); and at least 0.2 vinyls per 1000 carbons; and the rheology-modified polyolefin elastomer has an I2 of 12.5 or more 10 It has / I2, where I2 is measured according to ASTM D1238 (190℃, 2.16 kg), and I 10 It is measured according to ASTM D1238 (190℃, 10 kg).

[0270] According to the 50th aspect of the present disclosure, a method for preparing a crosslinkable polyolefin elastomer formulation comprises the step of forming a second composition comprising: a rheology-modified polyolefin elastomer prepared using any one of the methods of the 1st to 47th aspects; and a second organic peroxide in an amount of 0.1% to 2% by weight based on the combined weight of the rheology-modified polyolefin elastomer and the second organic peroxide.

[0271] The 51st embodiment comprises the 50th embodiment, wherein the second organic peroxide comprises one or more of tert-butylperoxy 2-ethylhexyl carbonate (TBEC), tert-amylperoxy 2-ethylhexyl carbonate (TAEC), 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonan and 1,1-di-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane.

[0272] The 52nd embodiment comprises either the 50th or 51st embodiment, and the 2nd composition further comprises a crosslinking aid.

[0273] The 53rd embodiment comprises the 52nd embodiment, and the crosslinking aid comprises one or more of trialyl cyanurate (TAC), trialyl phosphate (TAP), trialyl isocyanurate (TAIC), 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (vinyl D4), N,N,N′,N′,N″,N″-hexaallyl-1,3,5-triazine-2,4,6-triamine, trialyl trimellitate, trimethylolpropane triacylate (TMPTA), and trimethylolpropane trimethylacrylate (TMPTMA).

[0274] The 54th embodiment comprises any one of the 50th to 53rd embodiments, and the 2nd composition further comprises a silane coupling agent.

[0275] The 55th embodiment includes the 54th embodiment, and the silane coupling agent comprises one or more of vinyltrimethoxysilane (VTMS), 3-(trimethoxysilyl)propylmethacrylate, and tetraethoxysilane (TEOS).

[0276] The 56th embodiment comprises any one of the 50th to 53rd embodiments, and the step of forming the second composition comprises immersing an additive in a rheology-modified polyolefin elastomer to form a peroxide-immersed rheology-modified polyolefin elastomer, wherein the additive comprises a second organic peroxide; optionally a crosslinking aid; and optionally a silane coupling agent.

[0277] The 57th embodiment comprises the 56th embodiment, wherein the additive is immersed in the rheology-modified polyolefin elastomer at a second immersion temperature of 80°C or lower for a second immersion period of 0.5 hours or more.

[0278] The 58th embodiment comprises any one of the 50 to 57 embodiments, wherein a rheology-modified polyolefin elastomer is prepared using any one of the 17 to 29 embodiments, wherein the melt index (I2) of the polyolefin elastomer is greater than or equal to 0.5 dg / min and less than 12 dg / min; the organic peroxide has a 1-hour half-life temperature of up to 140°C; and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 7.7 minutes or less, T90 is measured according to ASTM D5289 (150°C), and T90 is defined as the time required to reach 90% of the maximum torque (MH) measured during the test interval.

[0279] The 59th embodiment includes the 58th embodiment, and the second organic peroxide is tert-amylperoxy 2-ethylhexyl carbonate (TAEC).

[0280] The 60th embodiment comprises any one of the 50th to 57th embodiments, wherein a rheology-modified polyolefin elastomer is prepared using a method of any one of the 17th to 29th embodiments, wherein the melt index (I2) of the polyolefin elastomer is 12 dg / min or more and 50 dg / min or less; and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 8.5 minutes or less, T90 is measured according to ASTM D5289 (150°C), and T90 is defined as the time required to reach 90% of the maximum torque (MH) measured during the test interval.

[0281] The 61st embodiment includes the 60th embodiment, and the second organic peroxide is tert-amylperoxy 2-ethylhexyl carbonate (TAEC).

[0282] The 62nd embodiment comprises any one of the 50 to 57 embodiments, wherein a rheology-modified polyolefin elastomer is prepared using any one of the 17 to 29 embodiments, wherein the melt index (I2) of the polyolefin elastomer is greater than or equal to 0.5 dg / min and less than 12 dg / min; the organic peroxide has a half-life temperature of 1 hour at a maximum of 140°C; and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 11.8 minutes or less, T90 is measured according to ASTM D5289 (150°C), and T90 is defined as the time required to reach 90% of the maximum torque (MH) measured during the test interval.

[0283] The 63rd embodiment includes the 62nd embodiment, and the second organic peroxide is tert-butylperoxy 2-ethylhexyl carbonate (TBEC).

[0284] The 64th embodiment comprises any one of the 50 to 57 embodiments, wherein a rheology-modified polyolefin elastomer is prepared using any one of the 17 to 29 embodiments, wherein the melt index (I2) of the polyolefin elastomer is 12 dg / min or more and 50 dg / min or less; and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 12.7 minutes or less, T90 is measured according to ASTM D5289 (150°C), and T90 is defined as the time required to reach 90% of the maximum torque (MH) measured during the test interval.

[0285] The 65th embodiment includes the 64th embodiment, and the second organic peroxide is tert-butylperoxy 2-ethylhexyl carbonate (TBEC).

[0286] The 66th embodiment comprises any one of the 50 to 57 embodiments, wherein a rheology-modified polyolefin elastomer is prepared using any one of the 38 to 41 embodiments, wherein the melt index (I2) of the polyolefin elastomer is 0.5 dg / min or more and less than 12 dg / min; and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 8.2 minutes or less, T90 is measured according to ASTM D5289 (150°C), and T90 is defined as the time required to reach 90% of the maximum torque (MH) measured during the test interval.

[0287] The 67th embodiment includes the 66th embodiment, and the second organic peroxide is tert-amylperoxy 2-ethylhexyl carbonate (TAEC).

[0288] The 68th embodiment comprises any one of the 50 to 57 embodiments, wherein a rheology-modified polyolefin elastomer is prepared using any one of the 38 to 41 embodiments, wherein the melt index (I2) of the polyolefin elastomer is 12 dg / min or more and less than 50 dg / min; and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 11.2 minutes or less, T90 is measured according to ASTM D5289 (150°C), and T90 is defined as the time required to reach 90% of the maximum torque (MH) measured during the test interval.

[0289] The 69th embodiment includes the 68th embodiment, and the second organic peroxide is tert-amylperoxy 2-ethylhexyl carbonate (TAEC).

[0290] The 70th embodiment comprises any one of the 50th to 57th embodiments, wherein a rheology-modified polyolefin elastomer is prepared using any one of the 38th to 41st embodiments, wherein the melt index (I2) of the polyolefin elastomer is 0.5 dg / min or more and less than 12 dg / min; and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 12.6 minutes or less, T90 is measured according to ASTM D5289 (150°C), and T90 is defined as the time required to reach 90% of the maximum torque (MH) measured during the test interval.

[0291] The 71st embodiment includes the 70th embodiment, and the second organic peroxide is tert-butylperoxy 2-ethylhexyl carbonate (TBEC).

[0292] The 72nd embodiment comprises any one of the 50 to 57 embodiments, wherein a rheology-modified polyolefin elastomer is prepared using a method of any one of the 38 to 41 embodiments, wherein the melt index (I2) of the polyolefin elastomer is 12 dg / min or more and less than 50 dg / min; and the crosslinkable polyolefin elastomer formulation has a curing time (T90) of 16.8 minutes or less, T90 is measured according to ASTM D5289 (150°C), and T90 is defined as the time required to reach 90% of the maximum torque (MH) measured during the test interval.

[0293] The 73rd embodiment includes the 72nd embodiment, and the second organic peroxide is tert-butylperoxy 2-ethylhexyl carbonate (TBEC).

[0294] The 74th embodiment comprises a crosslinkable polyolefin elastomer formulation prepared using any one of the methods of the 50th to 73rd embodiments.

[0295] According to the 75th aspect of the present disclosure, a crosslinkable polyolefin elastomer formulation comprises a rheology-modified polyolefin elastomer and 0.1% to 2% by weight of a second organic peroxide based on the combined weight of the rheology-modified polyolefin elastomer and the second organic peroxide, wherein the rheology-modified polyolefin elastomer has a density of 0.860 to 0.900 g / cc; a melt index (I2) of 0.5 to 50 dg / min (wherein I2 is measured according to ASTM D1238 (190°C, 2.16 kg); and a polyolefin elastomer having at least 0.2 vinyls per 1000 carbons; A first composition is prepared by forming a composition comprising 0.01% to 0.3% by weight of organic peroxide based on the combined weight of the polyolefin elastomer and the organic peroxide.

[0296] The 76th embodiment comprises a crosslinked polyolefin elastomer prepared in a crosslinkable polyolefin elastomer formulation of either the 74th or 75th embodiment.

[0297] The 77th embodiment includes the 76th embodiment, wherein the cross-linked polyolefin elastomer is prepared by heat, irradiation, electron beam radiation, or ultraviolet (UV) radiation.

[0298] According to the 78th aspect of the present disclosure, the article comprises a cross-linked polyolefin elastomer of either the 76th or 77th aspect.

[0299] The 79th embodiment includes the 78th embodiment, and the article is a multilayer film.

[0300] The 80th embodiment includes the 78th embodiment, and the article is a packaging material for a photovoltaic module.

[0301] Throughout this specification, references to “one embodiment,” “a specific embodiment,” “various embodiments,” “one or more embodiments,” or “an embodiment” mean that a specific feature, structure, material, or feature described in connection with an embodiment is included in at least one embodiment of this specification. Accordingly, the appearance of phrases such as “in an embodiment,” “in one or more embodiments,” “in a specific embodiment,” “in various embodiments,” “in one embodiment,” or “in one embodiment” at various locations throughout this specification does not necessarily refer to the same embodiment, nor does it refer to only one embodiment. Furthermore, a specific feature, structure, material, or feature may be combined in any suitable manner in one or more embodiments.

[0302] Although specific embodiments of the present disclosure are illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the present disclosure. Accordingly, the appended claims are intended to cover all such changes and modifications that fall within the scope of the present disclosure.

Claims

Claim 1 A method for manufacturing a rheology-modified polyolefin elastomer, comprising the step of forming a first composition, It is a polyolefin elastomer, but, Density of 0.860 to 0.900 g / cc; A melt index (I2) of 0.5 to 50 dg / min (wherein I2 is measured according to ASTM D1238 (190°C, 2.16 kg); and A polyolefin elastomer containing at least 0.2 vinyl units per 1,000 carbons; and A method comprising: forming a first composition comprising 0.01% to 0.3% by weight of an organic peroxide based on the combined weight of the polyolefin elastomer and the organic peroxide; and decomposing at least 75% by weight of the organic peroxide in the first composition. Claim 2 In claim 1, the rheology-modified polyolefin elastomer has an I of 8.5 or higher 10 With / I2, here I 10 The method measured according to ASTM D1238 (190℃, 10 kg). Claim 3 In claim 1, the rheology-modified polyolefin elastomer has an I of 12.5 or higher 10 With / I2, here I 10 The method measured according to ASTM D1238 (190℃, 10 kg). Claim 4 A method according to any one of claims 1 to 3, wherein the polyolefin elastomer has an unsaturation of 0.3 or more per 1,000 carbon atoms. Claim 5 A method according to any one of claims 1 to 4, wherein the polyolefin elastomer has a percentage of vinyl at a total degree of unsaturation of 50% or more. Claim 6 A method according to any one of claims 1 to 5, wherein the polyolefin elastomer has an oligomer level of less than 5000 ppm. Claim 7 A method according to any one of claims 1 to 6, wherein the first composition comprises 0.03 weight% to 0.2 weight% of an organic peroxide based on the combined weight of the polyolefin elastomer and the organic peroxide. Claim 8 A method according to any one of claims 1 to 7, wherein the organic peroxide comprises one or more of tert-butylperoxy 2-ethylhexyl carbonate (TBEC), tert-amylperoxy 2-ethylhexyl carbonate (TAEC), 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonan and 1,1-di-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane. Claim 9 A method according to any one of claims 1 to 8, wherein the melt index (I2) of the polyolefin elastomer is 0.5 to 35 dg / min. Claim 10 A method according to any one of claims 1 to 9, wherein the step of forming the first composition comprises immersing the organic peroxide in a pellet comprising a polyolefin elastomer to form a peroxide-immersed polyolefin elastomer pellet. Claim 11 In claim 10, the method wherein the immersion is performed at an immersion temperature of 80°C or lower for an immersion time of 0.5 hours or more. Claim 12 A method according to claim 10 or 11, wherein the step of decomposing at least 75 weight percent of the organic peroxide in the first composition comprises melt blending the peroxide-immersed polyolefin elastomer pellets. Claim 13 A method according to any one of claims 1 to 9, wherein the step of forming the first composition comprises adding the polyolefin elastomer and the organic peroxide to a continuous mixer or a batch mixer, and the step of decomposing at least 75 weight percent of the organic peroxide in the first composition comprises melt blending the polyolefin elastomer and the organic peroxide. Claim 14 In any one of claims 1 to 13, the polyolefin elastomer is prepared by solution polymerizing ethylene and optionally an α-olefin comonomer in the presence of a precatalyst having the following structure (I), and In the above formula, M is Zr or Hf, the metal is in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is an independently selected monodentate ligand; the total catalyst is charge-neutral; and R 1 and R 16 At least one of them is selected from the group consisting of structure (II), structure (III) and structure (IV): In the above structure, R 31-35 , R 41-48 , and R 51-59 is independently -H, C1-C 40 Hydrocarbyl, C1-C 40 Heterohydrocarbil, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or selected from halogen, and R C C1-C independently 40 Selected from hydrocarbil; R 3 and R 14 C1-C independently 40 It is hydrocarbyl or hydrogen; R 6 and R 11 C1-C independently 40 It is hydrocarbyl or hydrogen; R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 and R 15 is C1-C 40 Hydrocarbyl, C1-C 40 Heterohydrocarbyl, ―Si(R C )3, independently selected from the group consisting of halogen atoms, hydrogen atoms, and combinations thereof; R 17 and R 18 is independently C1-C3 hydrocarbylene; R 19 and R 20 C1-C independently 40 Hydrocarbyl or hydrogen, method. Claim 15 A method according to any one of claims 1 to 14, wherein the polyolefin elastomer is an ethylene / alpha-olefin copolymer. Claim 16 In claim 14 or 15, the melt index (I2) of the polyolefin elastomer is 0.5 dg / min or more and less than 12 dg / min; and the rheology-modified polyolefin elastomer has a rheology ratio (V) of 30 or more and 100 or less. 0.1 / V 100 Having ),V 0.1 is the complex viscosity of a rheology-modified polyolefin elastomer measured at 120°C at 0.1 radians / sec; V 100 Method, which is the complex viscosity of a rheology-modified polyolefin elastomer measured at 120°C at 100 radians / sec. Claim 17 In claim 14 or 15, the melt index (I2) of the polyolefin elastomer is 12 dg / min or more and 50 dg / min or less; and the rheology-modified polyolefin elastomer has a rheology ratio (V) of 12 or more and 50 or less. 0.1 / V 100 Having ),V 0.1 is the complex viscosity of a rheology-modified polyolefin elastomer measured at 120°C at 0.1 radians / sec; V 100 Method, which is the complex viscosity of a rheology-modified polyolefin elastomer measured at 120°C at 100 radians / sec. Claim 18 In any one of claims 14 to 16, the melt index (I2) of the polyolefin elastomer is 0.5 dg / min or more and less than 12 dg / min; and the rheology-modified polyolefin elastomer has an I2 of 14 or more and 25 or less. 10 With / I2, here I 10 The method measured according to ASTM D1238 (190℃, 10 kg). Claim 19 In any one of claims 14, 15 and 17, the melt index (I2) of the polyolefin elastomer is 12 dg / min or more and 50 dg / min or less; and the rheology-modified polyolefin elastomer has an I of 10.0 or more and 25 or less. 10 With / I2, here I 10 The method measured according to ASTM D1238 (190℃, 10 kg). Claim 20 In any one of claims 1 to 13, the polyolefin elastomer is formula A 1 L 1 It is manufactured from an unsaturated polyolefin, and the method is 1) (a1) a monomer component, (b1) a chain transfer agent component, and (c1) a catalyst component including a precatalyst, are combined to form a solution, and more than 10 mol% and less than or equal to 99 mol% of the (a1) monomer component in the solution are polymerized; 2) Step of heating the above solution; and 3) Chemical formula A above 1 L 1 The method comprises the step of recovering a product comprising a polyolefin component including an unsaturated polyolefin, wherein the (b1) chain transfer agent component comprises an aluminum alkyl of the formula Al(d)3, and d is independently C1 to C at each appearance 10 It is an alkyl group; L 1 is a polyolefin; A 1 Silver vinyl group, chemical formula CH2=C(Y 1 )- vinylidene group, chemical formula Y 1 The vinylene group of CH=CH-, vinyl group and chemical formula Y 1 A mixture of vinylene groups of CH=CH-, chemical formula CH2=C(Y 1 A mixture of vinylidene groups of )-, chemical formula CH2=C(Y 1 The vinylidene group of )- and the chemical formula Y 1 A mixture of vinylene groups of CH=CH-, and vinyl groups, chemical formula CH2=C(Y 1 )-'s vinylidene group, and chemical formula Y 1 Selected from the group consisting of mixtures of CH=CH- vinylene groups; Y 1 ...in each case, independently, C1 to C 30 Hydrocarbyl, method. Claim 21 A rheology-modified polyolefin elastomer manufactured using the method of any one of claims 1 to 20. Claim 22 A rheology-modified polyolefin elastomer comprising a reaction product of a polyolefin elastomer and an organic peroxide, wherein the polyolefin elastomer is Density of 0.860 to 0.900 g / cc; A melt index (I2) of 0.5 to 50 dg / min (wherein I2 is measured according to ASTM D1238 (190°C, 2.16 kg); and Rheology-modified polyolefin elastomers having more than 0.2 vinyl groups per 1,000 carbons have an I of 12.5 or higher 10 It has / I2, where I2 is measured according to ASTM D1238 (190℃, 2.16 kg), and I 10 rheology-modified polyolefin elastomer measured according to ASTM D1238 (190°C, 10 kg). Claim 23 A method for preparing a crosslinkable polyolefin elastomer formulation, comprising the step of forming a second composition, A rheology-modified polyolefin elastomer produced using the method of any one of claims 1 to 20; and A method comprising the step of forming the second composition comprising 0.1% to 2% by weight of the second organic peroxide based on the combined weight of the rheology-modified polyolefin elastomer and the second organic peroxide. Claim 24 As a crosslinkable polyolefin elastomer formulation, as a rheology-modified polyolefin elastomer, As a step of forming a first composition, It is a polyolefin elastomer, but, Density of 0.860 to 0.900 g / cc; A melt index (I2) of 0.5 to 50 dg / min (wherein I2 is measured according to ASTM D1238 (190°C, 2.16 kg); and The above polyolefin elastomer having at least 0.2 vinyls per 1,000 carbons; and A step of forming the first composition comprising 0.01% to 0.3% by weight of an organic peroxide based on the combined weight of the polyolefin elastomer and the organic peroxide; and A crosslinkable polyolefin elastomer formulation comprising: a rheology-modified polyolefin elastomer prepared by the step of decomposing at least 75 weight% of the organic peroxide in the first composition; and a second organic peroxide in an amount of 0.1 weight% to 2 weight% based on the combined weight of the rheology-modified polyolefin elastomer and the second organic peroxide. Claim 25 A crosslinked polyolefin elastomer prepared from the crosslinkable polyolefin elastomer formulation of claim 24.

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