Method for preparing olefin-acrylate block copolymers using ATRP

Abstract

The present disclosure relates to a method for preparing an olefin-acrylate block copolymer, the method comprising: a) performing atom transfer radical polymerization (ATRP) by combining ATRP materials including an acrylate monomer, an initiator having a radically transferable atom or group, a transition metal compound, and a ligand, thereby forming a macroinitiator; and b) combining reactive materials including an alpha-substituted acrylate and the macroinitiator, thereby forming the olefin-acrylate block copolymer.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Application No. 63 / 018272, filed on 30 April 2020, which is incorporated herein by reference in its entirety. [Background technology]

[0002] This disclosure relates to a method for synthesizing olefin-acrylate block copolymers using atom transfer radical polymerization (ATRP) of acrylate monomers to prepare functionalized polyacrylates that subsequently react with alpha-substituted acrylate monomers (such as alpha-(alkyl)acrylate monomers or alpha-(polymeric)acrylate monomers). In this method, alpha-substituted acrylate monomers suitable for reactions using standard ATRP methods well known in the art are employed as monomers that react with the polyacrylate produced by ATRP to form olefin-acrylate block copolymers. This method and the resulting olefin-acrylate block copolymers have not been realized to date. [Overview of the Initiative]

[0003] This disclosure relates to a method for preparing olefin-acrylate block copolymers, the method being described below: a) Performing atomic transfer radical polymerization (ATRP) by combining an acrylate monomer, an initiator having radical-transferable atoms or groups, a transition metal compound, and a ligand, thereby forming a macroinitiator, b) Combining reaction materials containing alpha-substituted acrylates and macroinitiators to form olefin-acrylate block copolymers, Includes.

[0004] This disclosure further relates to olefin-acrylate block copolymers prepared by the present method. [Brief explanation of the drawing]

[0005] [Figure 1A] The 1H NMR and 13C NMR spectra of Example 1 are shown below. [Figure 1B] The 1H NMR and 13C NMR spectra of Example 1 are shown below. [Figure 1C] The GCMS spectrum of Example 1 is shown. [Figure 1D] The GCMS spectrum of Example 1 is shown. [Figure 2A] The 1H NMR and diffusion NMR spectra for Example 2 are shown below. [Figure 2B] The 1H NMR and diffusion NMR spectra for Example 2 are shown below. [Figure 3A] The 1H NMR spectrum and diffusion NMR spectrum for Example 3 are shown below. [Figure 3B] The 1H NMR spectrum and diffusion NMR spectrum for Example 3 are shown below. [Modes for carrying out the invention]

[0006] definition All references to the periodic table in this specification refer to the periodic table published and copyrighted by CRC Press, Inc. in 2003. Furthermore, any reference to a group(s) refers to the group(s) as they appear in the periodic table using the IUPAC system for numbering groups.

[0007] Unless otherwise stated, suggested by the context, or customary in the art, all parts and percentages are based on weight.

[0008] For the purposes of U.S. patent practice, the contents of any patents, patent applications, or publications referenced herein are incorporated herein by reference in their entirety, particularly with respect to the disclosure of synthesis techniques, definitions (to the extent that they are not inconsistent with any definitions provided herein), and general knowledge in the art (or their equivalent U.S. editions are incorporated herein by reference).

[0009] Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit, including the lower and upper limits. In the case of ranges containing explicit values ​​(e.g., 1, or 2, or 3 to 5, or 6, or 7), any sub-ranges between any two explicit values ​​are included (e.g., sub-ranges such as 1 to 2, 2 to 6, 5 to 7, 3 to 7, 5 to 6, etc.). Numerical ranges disclosed herein further include fractions between any two explicit values.

[0010] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the existence of any additional components, processes, or procedures, whether or not they are specifically disclosed. In contrast, the term “essentially consisting of” excludes any other components, processes, or procedures from the scope of any subsequent detail, except those not essential to operability. The term “consisting of” excludes any components, processes, or procedures not specifically described or enumerated. The term “or” refers to the enumerated items individually and in any combination, unless otherwise specified.

[0011] As used herein, terms such as "hydrocarbyl" and "hydrocarbyl group" refer to compounds composed entirely of hydrogen and carbon, including aliphatic, aromatic, acyclic, cyclic, polycyclic, branched, unbranched, saturated, and unsaturated compounds. Terms such as "hydrocarbyl," "hydrocarbyl group," "alkyl," "alkyl group," "aryl," and "aryl group" are intended to include all possible isomers, including all structural or stereoisomers.

[0012] The term "cyclic" refers to a set of atoms in a polymer or compound, such a set of atoms comprising one or more rings. Therefore, the term "cyclic hydrocarbyl group" refers to a hydrocarbyl group containing one or more rings. As used herein, a "cyclic hydrocarbyl group" may contain acyclic (linear or branched) moieties in addition to one or more rings.

[0013] The term "polymer" refers to a material prepared by reacting (i.e., polymerizing) a set of monomers, which may be a set of homogeneous (i.e., only one type) or heterogeneous (i.e., two or more types) monomers. As used herein, the term polymer includes the term "homopolymer," which refers to a polymer prepared from a set of homogeneous monomers, and the term "interpolymer," as defined below.

[0014] The term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. This term includes both "copolymers," i.e., polymers prepared from two different types of monomers, and polymers prepared from three or more different types of monomers, such as terpolymers and tetrapolymers. The term also encompasses all forms of interpolymers, including random, block, homogeneous, and heterogeneous types.

[0015] "Polyolefin" is a polymer produced from the polymerization of olefins as monomers, where olefin monomers are linear, branched, or cyclic compounds of carbon and hydrogen having at least one double bond. Therefore, as used herein, the term "polyolefin" includes and encompasses the terms "ethylene-based polymer," "propylene-based polymer," "ethylene homopolymer," "propylene homopolymer," "ethylene / alpha-olefin interpolymer," "ethylene / alpha-olefin copolymer," "ethylene / alpha-olefin multiblock interpolymer," "block complex," "specific block complex," "crystalline block complex," "propylene / alpha-olefin interpolymer," and "propylene / alpha-olefin copolymer."

[0016] An "ethylene-based polymer" is a polymer that, based on the weight of the polymer, contains a majority of polymerized ethylene and may optionally further contain polymer units of at least one comonomer. An "ethylene-based interpolymer" is an interpolymer that, based on the weight of the interpolymer, contains a majority of ethylene in polymerized form and may further contain polymer units of at least one comonomer. An "ethylene homopolymer" is a polymer that contains repeating units derived from ethylene but does not exclude residual amounts of other components.

[0017] As used herein, the term “ethylene / alpha-olefin interpolymer” refers to a polymer comprising, in polymeric form, a majority by weight percent of ethylene (based on the weight of the interpolymer) and at least one comonomer that is an alpha-olefin. Ethylene / alpha-olefin interpolymers may be random or block interpolymers. The terms “ethylene / alpha-olefin copolymer” and “ethylene / alpha-olefin multiblock interpolymer” are encompassed by the term “ethylene / alpha-olefin interpolymer.”

[0018] As used herein, the term “ethylene / alpha-olefin copolymer” refers to a copolymer comprising, in polymeric form, a majority by weight percent of ethylene (based on the weight of the copolymer) and a comonomer that is alpha-olefin, where ethylene and alpha-olefin are the only two monomer types. Ethylene / alpha-olefin copolymers may be random or block copolymers.

[0019] As used herein, “ethylene / alpha-olefin multiblock interpolymer” or “olefin block copolymer” refers to an interpolymer comprising ethylene and one or more copolymerizable alpha-olefin comonomers in a polymerized form, characterized by multiple blocks or segments of two or more (preferably three or more) polymerized monomer units, blocks or segments having different chemical or physical properties. Specifically, this term refers to a polymer comprising two or more (preferably three or more) chemically distinct regions or segments (referred to as “blocks”) linked in a linear manner, i.e., a polymer comprising chemically distinct units that are end-to-end linked (covalently bonded) with respect to the polymerized functional groups, rather than in a pendant or grafted manner. Blocks differ in the amount or type of comonomers incorporated therein, density, amount and type of crystallinity (e.g., polyethylene vs. polypropylene), crystal size resulting from polymers of such composition, type or degree of stereoregularity (isotactic or syndiotactic), regional regularity or regional irregularity, amount of branching including long-chain branching or hyperbranching, uniformity, and / or any other chemical or physical properties. Block copolymers are characterized by unique distributions of both polymer polydispersity (PDI or Mw / Mn) and block length distribution, for example, based on the effect of using a shuttling agent in combination with a catalyst system. Non-limiting examples of the olefin block copolymers of this disclosure and processes for preparing them are disclosed in U.S. Patents 7,858,706(B2), 8,198,374(B2), 8,318,864(B2), 8,609,779(B2), 8,710,143(B2), 8,785,551(B2), and 9,243,090(B2), the entirety of which is incorporated herein by reference.

[0020] The term "block composite" (BC) refers to a polymer comprising three polymer components: (i) an ethylene-based polymer (EP) (soft copolymer) having an ethylene content of 10 mol% to 90 mol% based on the total moles of polymerized monomer units in the ethylene-based polymer (EP); (ii) an alpha-olefin-based polymer (AOP) (hard copolymer) having an alpha-olefin content of more than 90 mol% based on the total moles of polymerized monomer units in the alpha-olefin-based polymer (AOP); and (iii) a block copolymer (diblock copolymer) having an ethylene block (EB) and an alpha-olefin block (AOB), where the ethylene block of the block copolymer has the same composition as the EP of component (i) of the block composite, and the alpha-olefin block of the block copolymer has the same composition as the AOP of component (ii) of the block composite. In addition, the compositional distribution between the amounts of EP and AOP in the block composite will be essentially the same as the compositional distribution between the corresponding blocks in the block copolymer. Non-limiting examples of the block composites of this disclosure and processes for preparing them are disclosed in U.S. Patents 8,686,087 and 8,716,400, which are incorporated herein by reference in their entirety.

[0021] The term "specified block composite" (SBC) refers to a polymer comprising three polymer components: (i) an ethylene-based polymer (EP) (soft copolymer) having an ethylene content of 78 mol% to 90 mol% based on the total moles of polymerized monomer units in the ethylene-based polymer (EP); (ii) an alpha-olefin-based polymer (AOP) (hard copolymer) having an alpha-olefin content of 61 mol% to 90 mol% based on the total moles of polymerized monomer units in the alpha-olefin-based polymer (AOP); and (iii) a block copolymer (diblock copolymer) having an ethylene block (EB) and an alpha-olefin block (AOB), where the ethylene block of the block copolymer has the same composition as the EP of component (i) of the specified block composite, and the alpha-olefin block of the block copolymer has the same composition as the AOP of component (ii) of the specified block composite. In addition, the compositional distribution between the amounts of EP and AOP in the specified block composite will be essentially the same as the compositional distribution between the corresponding blocks in the block copolymer. Non-limiting examples of specific block complexes of this disclosure, as well as processes for preparing them, are disclosed in International Publication No. 2017 / 044547, which is incorporated herein by reference in its entirety.

[0022] The term "crystalline block complex" ("CBC") refers to a polymer comprising three components: (i) a crystalline ethylene-based polymer (CEP) with an ethylene content exceeding 90 mol% based on the total number of moles of polymerized monomer units in the CEP; (ii) a crystalline alpha-olefin-based copolymer (CAOP) having an alpha-olefin content exceeding 90 mol% based on the total number of moles of polymerized monomer units in the CAOP; and (iii) a block copolymer containing a crystalline ethylene block (CEB) and a crystalline alpha-olefin block (CAOB), where the CEB of the block copolymer has the same composition as the CEP of component (i) of the crystalline block complex, and the CAOB of the block copolymer has the same composition as the CAOP of component (ii) of the crystalline block complex. In addition, the compositional distribution between the amounts of CEP and CAOP in the crystalline block complex will be essentially the same as the compositional distribution between the corresponding blocks in the block copolymer. Non-limiting examples of the crystalline block composites of this disclosure and processes for preparing them are disclosed in U.S. Patent No. 8,822,598(B2) and International Publication No. 2016 / 01028961(A1), which are incorporated herein by reference in their entirety.

[0023] A "propylene-based polymer" is a polymer that, based on the weight of the polymer, contains a majority of polymerized propylene and may optionally further contain polymer units of at least one comonomer. A "propylene-based interpolymer" is an interpolymer that, based on the weight of the interpolymer, contains a majority of propylene in polymerized form and may further contain polymer units of at least one comonomer. A "propylene homopolymer" is a polymer that contains repeating units derived from propylene but does not exclude residual amounts of other components.

[0024] As used herein, the term “propylene / alpha-olefin interpolymer” refers to a polymer comprising, in polymeric form, a majority by weight percent of propylene (based on the weight of the interpolymer) and at least one comonomer that is an alpha-olefin (where ethylene is considered an alpha-olefin). Propylene / alpha-olefin interpolymers may be random or block interpolymers. The term “propylene / alpha-olefin interpolymer” includes the term “propylene / alpha-olefin copolymer.”

[0025] As used herein, the term “propylene / alpha-olefin copolymer” refers to a copolymer comprising, in polymeric form, a majority by weight percent of propylene (based on the weight of the copolymer) and a comonomer that is alpha-olefin, where propylene and alpha-olefin are the only two monomer types. Propylene / alpha-olefin copolymers may be random or block copolymers.

[0026] Terms such as "polymeric" and "polymeric group" refer to polymers that lack one hydrogen atom.

[0027] Terms such as "polyolefin" and "polyolefin group" refer to polyolefins that lack one hydrogen atom.

[0028] Atomic transfer radical polymerization (ATRP) Step a) of the method of this disclosure relates to forming a functionalized polyacrylate via ATRP. Specifically, step a) of the method relates to performing ATRP by combining an ATRP material comprising an acrylate monomer, an initiator having a radical-mobile atom or group, a transition metal compound, and a ligand, thereby forming a macroinitiator. Suitable techniques and conditions for ATRP in step a) are known in the art, for example, as described in Macromolecules, 33, 4039-4047, 2000 and U.S. Patent No. 5,945,491, which are incorporated herein by reference. In fact, each of the initiators, transition metal compounds, and ligands for ATRP materials is known in the art and is disclosed, for example, in U.S. Patent No. 5,945,491.

[0029] In a particular embodiment, the acrylate monomer in step a) has formula (III), [ka] In the formula, R1 is hydrogen or a C1-C30 hydrocarbyl group, and R2 is hydrogen or a methyl group.

[0030] In certain embodiments, R1 is a C1-C30 hydrocarbyl group that may be linear, branched, or cyclic. In further embodiments, R1 is a C1-C30 alkyl group that may be linear, branched, or cyclic. For example, R1 may be a linear, branched, or cyclic alkyl group containing 1-30 carbon atoms, or 1-20 carbon atoms, or 1-10 carbon atoms, or 1-8 carbon atoms.

[0031] In a particular embodiment, the initiator has formula (IV): [ka] During the ceremony, X is a halide (preferably Cl, Br, or I), OR 10 , SR 14 ,SeR 14 -SCN (thiocyanate), OC (=O)R14 , OP(=O)R 14 , OP(=O)(OR 14 )2, OP(=O)OR 14 , O-N(R 14 )2, and S-C(=S)N(R 14 )2 selected from the group consisting of, R 14 is an aryl or linear or branched C1-C20 (preferably C1-C10) alkyl group, or when the N(R 14 )2 group is present, the two R 14 groups can be bonded to form a 5-, 6- or 7-membered heterocycle, R 10 is alkyl of 1 to 20 carbon atoms, each of the hydrogen atoms thereof may be independently substituted with a halide, R11, R12, and R13 are each independently H, halide, C1-C20 alkyl (preferably C1-C10 alkyl, more preferably C1-C6 alkyl), C3-C8 cycloalkyl, C(=Y)R 5 , C(=Y)NR 6 R 7 , COCl, OH (preferably only one of R11, R12 and R13 is OH), CN, C2-C20 alkenyl or alkynyl (preferably C2-C6 alkenyl or alkynyl, more preferably vinyl), oxiranyl, glycidyl, aryl, heterocyclyl, aralkyl, aralkylene (aryl-substituted alkenyl, and alkenyl is vinyl which may be substituted with one or two C1-C6 alkyl groups and / or halogen atoms, preferably chlorine), C1-C6 alkyl in which one to all hydrogen atoms (preferably one) are substituted with halogen (preferably fluorine or chlorine in which one or more hydrogen atoms are substituted, preferably fluorine, chlorine or bromine in which one hydrogen atom is substituted), and C1-C4 alkoxy, aryl, heterocyclyl, C(=Y)R 6 , C(=Y)NR 6 R 7Selected from the group consisting of C1-C6 alkyl groups substituted with 1-3 substituents (preferably 1) selected from the group consisting of oxyranyl and glycidyl, and therefore, two or fewer of R11, R12 and R13 are H (preferably, one or fewer of R11, R12 and R13 are H), Y is NR 8 Or O (preferably O), and also, R 5 R is an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an aryloxy group, or a heterocyclyloxy group. 6 and R 7 is independently H or an alkyl group with 1 to 20 carbon atoms, or R 6 and R 7 These bond to each other to form a 3-6 membered ring by creating an alkylene group of 2-5 carbon atoms, R 8 These are H, linear or branched C1-C20 alkyl and aryl groups.

[0032] When an alkyl, cycloalkyl, or alkyl-substituted aryl group is selected as one of R11, R12, and R13, the alkyl group may be further substituted with a halogen. Thus, the initiator can function as a starting molecule for branched or star-shaped (co)polymers. A preferred example is a phenyl molecule in which one of R11, R12, and R13 is substituted with 1 to 5 C-C alkyl substituents, each of which may be independently further substituted with a halogen.

[0033] The transition metal compound in step a) of this disclosure may be any transition metal compound that can participate in the redox cycle with the initiator and resting polymer chain but does not directly form carbon-metal bonds with the polymer chain. A preferred transition metal compound is of formula M t Q+ X' Q It is of the form, and in the formula, M t Q+ is, Cu 1+ Cu 2+ Fe 2+ Fe 3+ , Ru 2+ , Ru3+ , Cr 2+ , Cr 3+ Mo 0 Mo + Mo 2+ Mo 3+ , W 2+ , W 3+ , Rh 3+ , Rh 4+ Co + CO 2+ Re 2+ Re 3+ Ni 0 Ni + Mn 3+ Mn 4+ , V 2+ , V 3+ Zn + Zn 2+ Au + Au 2+ Ag + and Ag 2+ X' may be selected from the group consisting of halogens, C1-C20 alkoxys, and (SO4). 1 / 2 (PO4) 1 / 3 (HPO4) 1 / 2 (H2PO4), triflate, SCN (thiocyanate), hexafluorophosphate, alkyl sulfonate, aryl sulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 14 , CN and R 15 Selected from the group consisting of CO2, R 14 As defined above, R 15 Q is a heteroaryl group that can be substituted 1 to 5 times (preferably 1 to 3 times) with H or a linear or branched C1-C20 alkyl group (preferably methyl), a benzoic acid derivative, an aryl, or a halogen, and Q is the formal charge of the metal (e.g., 0 ≤ Q ≤ 7).

[0034] In this disclosure, any transition metal compound is suitable, but transition metal halides such as copper iodide, copper bromide, or copper chloride are preferred.

[0035] Ligands suitable for use in the present disclosure include ligands having one or more nitrogen, oxygen, phosphorus, and / or sulfur atoms that can coordinate to a transition metal via a sigma bond, and ligands containing two or more carbon atoms that can coordinate to a transition metal via a pi bond. Preferred N-, O-, P-, and S-containing ligands can have one of the following formulas: R 16 -Z’-R 17 R 16 -Z’-(R 18 -Z’) L -R 17 In the formula, R 16 and R 17 are independently selected from the group consisting of H, C1-C20 alkyl, aryl, heterocyclyl, and C1-C6 alkyl substituted with C1-C6 alkoxy, C1-C4 dialkylamino, C(=Y)R 5 C=Y)R 6 R 7 and YC(=Y)R 8 where Y, R 5 R 6 R 7 and R 8 are as defined above, or R 16 and R 17 can combine to form a saturated, unsaturated or heterocyclic ring, Z’ is O, S, NR 19 or PR 19 where R 19 is selected from the same group as R 16 and R 17 Each R 18 is independently a divalent group selected from the group consisting of C2-C4 alkylene (alkanediyl) and C2-C4 alkenylene where the covalent bond to each Z’ is in an adjacent position (e.g., 1,2 configuration) or beta position (e.g., 1,3 configuration), and C3-C8 cycloalkanediyl, C3-C8 cycloalkenediyl, arenediyl and heterocyclylene where the covalent bond to each Z’ is in an adjacent position, L is from 1 to 6.​

[0036] In addition to the ligands described above, R 16 -Z’ and R 17 -Z’ each can form a ring with the R 18 group to which Z’ is attached and form a linked or fused heterocyclic system. Alternatively, when R 16 and / or R 17 is heterocyclyl, Z’ can be, in addition to the definition given above for Z’, a covalent bond (which may be single or double), CH2, or a 4- to 7-membered ring fused to R 16 and / or R 17 . Exemplary ring systems for this ligand include bipyridine, bipyrrole, 1,10-phenanthroline, cryptand, crown ether, etc., and Z’ is PR 19 , and R 19 can also be C1-C20-alkoxy.

[0037] Examples of suitable ligands include pyridine derivatives having substituents at the 2-position or at the 2- and 6-positions, such as carbonyl-containing moieties, imine-containing moieties, or thioketone-containing moieties.

[0038] Also, ligands suitable for use in the present disclosure include CO (carbon monoxide), porphyrin, and porphycene, and the latter two can be further substituted with 1 to 6 (preferably 1 to 4) halogen atoms, a C1-C6 alkyl group, a C1-C6-alkoxy group, a C1-C6 alkoxycarbonyl, an aryl group, a heterocyclyl group, and a C1-C6 alkyl group further substituted with 1 to 3 halogens.

[0039] Further ligands suitable for use in the present invention include compounds of the formula R 20 R 21 C(C(=Y)R 5 )2, where Y and R 5 are as defined above, and each of R 20 and R 21 is independently selected from the group consisting of H, halogen, C1-C20 alkyl, aryl, and heterocyclyl, and R 20and R 21 These can bond to form a C3-C8 cycloalkyl ring or a hydrogenated (i.e., reduced, non-aromatic, or partially or fully saturated) aromatic ring or heterocycle, any of which (except H and halogen) may be further substituted with 1-5, preferably 1-3, C1-C6 alkyl groups, C1-C6 alkoxy groups, halogen atoms and / or aryl groups. Preferably, R 20 and R 21 One of these is either H or a negative charge.

[0040] Additional suitable ligands include, for example, ethylenediamine and propylenediamine (both of which may be substituted 1 to 4 times on the amino nitrogen atom with a C1-C4 alkyl group or a carboxymethyl group); aminoethanol and aminopropanol (both of which may be substituted 1 to 3 times on the oxygen atom and / or nitrogen atom with a C1-C4 alkyl group); ethylene glycol and propylene glycol (both of which may be substituted once or twice on the oxygen atom with a C1-C4 alkyl group); and diglyme, triglyme, tetraglyme, etc.

[0041] Suitable carbon ligands include arenes and cyclopentadienyl ligands. Preferred carbon ligands include benzene (which can be substituted with 1 to 6 C1 to C4 alkyl groups, e.g., methyl groups) and cyclopentadienyl (which can be substituted with 1 to 5 methyl groups, or linked to a second cyclopentadienyl ligand via an ethylene or propylene chain). When cyclopentadienyl ligands are used, it may not be necessary to include a counteranion (X') in the transition metal compound.

[0042] Preferred ligands include unsubstituted and substituted pyridines and bipyridines, acetonitrile, (R 10 O) 3P, PR 10 3,1,10-Phenanthroline, Porphyrin, K 222Examples include cryptands such as 18-crown-6, crown ethers such as 18-crown-6, and nitrogen or sulfur analogs of crown ethers. The most preferred ligands are substituted bipyridines, bipyridines and (R 10 O)3P. Examples of such ligands (but not limited to these) include 2,2'-bipyridine, p-alkyl-substituted derivatives of 2,2'-bipyridine, or p-alkoxy-substituted derivatives of 2,2'-bipyridine.

[0043] The molar ratios of the initiator, transition metal compound, and ligand may be in the range of 1 / 0.01 / 0.02 to 1 / 4 / 12.

[0044] In a particular embodiment, the macroinitiator formed in step a) has formula (V): Polyacrylate-(X) y (V) During the ceremony, "Polyacrylate" refers to a polyacrylate derived from the ATRP of acrylate monomer (III), where X is as defined herein (preferably Cl, Br, or I), and y is between 1 and 100.

[0045] In certain embodiments, step a) of the method may be carried out in a neat state. In further embodiments, the ATRP material in step a) of the method further comprises a solvent.

[0046] In certain embodiments, step a) of the method is performed at a temperature suitable for ATRP. For example, step a) of the method may be performed at a temperature of 40 to 150°C, but is not limited to this.

[0047] The amount and ratio of ATRP material in step a) may be adjustable and are known to those skilled in the art.

[0048] Reaction with alpha-substituted acrylates Step b) of this method involves reacting the functionalized polyacrylate prepared in step a) with an alpha-substituted acrylate such as alpha(alkyl)acrylate or alpha(polymeric)acrylate to form an olefin-acrylate block copolymer. Specifically, step b) of this method involves combining a reaction material containing the alpha-substituted acrylate of formula (V) and a macroinitiator to form an olefin-acrylate block copolymer.

[0049] In a particular embodiment, the alpha-substituted acrylate has formula (II): [ka] In the formula, R is a C1-C26 hydrocarbyl group or a polyolefinyl group. R1 is either hydrogen or a C1-C30 hydrocarbyl group.

[0050] R1 may be any of the embodiments described above.

[0051] In certain embodiments, R is a C1-C26 hydrocarbyl group. In embodiments where R is a C1-C26 hydrocarbyl group, R can be a linear, branched, or cyclic C1-C26 alkyl group. For example, R can be a linear, branched, or cyclic alkyl group containing 1 to 26 carbon atoms, or 1 to 10 carbon atoms, or 1 to 8 carbon atoms.

[0052] In further embodiments, R is a polyolefin group. In certain embodiments, R is a polyolefin group that can be defined by the properties of RH, and RH has a number average molecular weight greater than 365 g / mol. In further embodiments, R is a polyolefin group that can be defined by the properties of RH, and RH has a number average molecular weight of 365 g / mol to greater than 10,000,000 g / mol, or 365 g / mol to greater than 5,000,000 g / mol, or 365 g / mol to greater than 1,000,000 g / mol, or 365 g / mol to greater than 750,000 g / mol, or 365 g / mol to greater than 500,000 g / mol, or 365 g / mol to greater than 250,000 g / mol.

[0053] In further embodiments, R is a polyolefinic group which may be defined by the properties of RH, and RH has a density of 0.850 to 0.965 g / cc, or 0.860 to 0.950 g / cc, or 0.865 to 0.925 g / cc.

[0054] In further embodiments, R is a polyolefinic group that can be defined by the properties of RH, and RH has a melt index (I2) of 0.01 to 2,000 g / 10 min, or 0.01 to 1,500 g / 10 min, or 0.1 to 1,000 g / 10 min, or 0.1 to 500 g / 10 min, or 0.1 to 100 g / 10 min.

[0055] In further embodiments, R is a polyolefinic group which may be defined by the properties of RH, and RH has a number-average molecular weight distribution (Mw / Mn or PDI) of 1 to 10, or 1 to 7, or 1 to 5, or 2 to 4.

[0056] In certain embodiments, R is an ethylene homopolymeric group containing units derived from ethylene.

[0057] In certain embodiments, R is an ethylene / alpha-olefin interpolymeryl group comprising ethylene and units derived from at least one C3-C30 alpha-olefin. The C3-C30 alpha-olefin may be, for example, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene.

[0058] In certain embodiments, R is an ethylene / alpha-olefin copolymeryl group containing units derived from ethylene and C3-C30 alpha-olefins. The C3-C30 alpha-olefins may be, for example, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene.

[0059] In certain embodiments, R is an ethylene / alpha-olefin multiblock interpolymeryl or olefin block copolymeryl group as defined herein.

[0060] In further embodiments, R is a polymeryl group of a block complex as defined herein, a specific block complex, or a crystalline block complex.

[0061] In certain embodiments, R is a propylene homopolymeric group containing units derived from propylene.

[0062] In certain embodiments, R is a propylene / alpha-olefin interpolymeric group comprising units derived from ethylene or propylene, which is a C3-C30 alpha-olefin, and at least one comonomer. The C3-C30 alpha-olefin may be, for example, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene.

[0063] In certain embodiments, R is a propylene / alpha-olefin copolymeryl group containing units derived from ethylene or propylene and comonomers, which are C3-C30 alpha-olefins. The C3-C30 alpha-olefins may be, for example, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene.

[0064] The alpha-substituted acrylate of formula (II) can be prepared by any preferred method. Non-limiting methods for preparing the alpha-substituted acrylate of formula (II) are disclosed in concurrently pending U.S. Provisional Patent Applications No. 62 / 954,941 and No. 62 / 954,956. For example, the alpha-substituted acrylate of formula (II) can be prepared by combining a material containing alpha-(halomethyl)acrylate with an organometallic compound of formula R2Zn or R3Al (wherein R is as defined herein). In such non-limiting methods, a nucleophilic substitution reaction occurs, where the halogen is a leaving group replaced by R in the organometallic compound of formula R2Zn or R3Al.

[0065] In certain embodiments, the olefin-acrylate block copolymer obtained by this method has formula (VI). [ka]

[0066] "Polyacrylate", R, R1, X, and y are as defined herein, and m is between 1 and 50.

[0067] As can be seen in formula (VI), the polymer structure of the olefin-acrylate block copolymers prepared by the method of the present disclosure can vary. Examples of polymer structures include linear diblock copolymers, hyperbranched diblock copolymers, polybranched diblock copolymers, and comb-like / brush-like diblock copolymers. For example, when a monofunctional ATRP initiator is used in step b) (y=1), a linear diblock copolymer is prepared by adding 1 equivalent of alpha-substituted acrylate to a macroinitiator, and a diblock copolymer having a comb-like polyolefin block is prepared by adding "m" equivalents of alpha-substituted acrylate to a macroinitiator.

[0068] In certain embodiments, step b) of the method may be carried out in a neat state. In further embodiments, the reactants in step b) of the method further include a solvent.

[0069] For example, although not limited to this, step b) of this method may be carried out at a temperature of 40 to 150°C.

[0070] The amount and ratio of the reactants in step b) may be adjustable and are known to those skilled in the art.

[0071] This method may, but is not limited to, the following scheme. [ka]

[0072] Specific embodiments of this disclosure include, but are not limited to, the following: 1. A method for preparing an olefin-acrylate block copolymer, a) Performing atomic transfer radical polymerization (ATRP) by combining an acrylate monomer, an initiator having radical-transferable atoms or groups, a transition metal compound, and a ligand, thereby forming a macroinitiator, b) Combining reaction materials containing alpha-substituted acrylates and macroinitiators to form olefin-acrylate block copolymers, Methods that include... 2. The alpha-substituted acrylate has formula (II), [ka] The acrylate monomer has formula (III), [ka] The initiator has formula (IV), [ka] The macroinitiator has formula (V), Polyacrylate-(X) y (V) The olefin-acrylate block copolymer has formula (VI), [ka] During the ceremony, Each R1 is independently either hydrogen or a C1-C30 hydrocarbyl group. Each R2 is independently either a hydrogen atom or a methyl group. Each R is independently a C1-C26 hydrocarbyl group or a polyolefinyl group. m is between 1 and 50. Each y is independently between 1 and 100. Each X is independently a halide (preferably Cl, Br, or I), OR 10 , SR 14 ,SeR 14 -SCN (thiocyanate), OC (=O)R 14 , OP(=O)R 14 , OP(=O)(OR 14 )2, OP(=O)OR 14 , ON(R 14 )2, and SC(=S)N(R 14 Selected from the group consisting of )2, R 14is an aryl or linear or branched C1-C20 (preferably C1-C10) alkyl group, or N(R 14 )When two units exist, two R 14 The groups can bond to form 5-membered, 6-membered, or 7-membered heterocycles, R 10 This is an alkyl group with 1 to 20 carbon atoms, and each of the hydrogen atoms may be independently substituted with a halide. R11, R12, and R13 are each independently H, halide, C1-C20 alkyl (preferably C1-C10 alkyl, more preferably C1-C6 alkyl), C3-C8 cycloalkyl, and C(=Y)R 5 , C(=Y)NR 6 R 7 COCl, OH (preferably only one of R11, R12, and R13 is OH), CN, C2-C20 alkenyl or alkynyl (preferably C2-C6 alkenyl or alkynyl, more preferably vinyl), oxyranyl, glycidyl, aryl, heterocyclyl, aralkyl, aralkylene (aryl-substituted alkenyls, and alkenyls are vinyl which can be substituted with one or two C1-C6 alkyl and / or halogen atoms, preferably chlorine), C1-C6 alkyls in which one to all hydrogen atoms (preferably one) are substituted with halogens (preferably fluorine or chlorine with one or more hydrogen atoms substituted, preferably fluorine, chlorine, or bromine with one hydrogen atom substituted), and C1-C4 alkoxy, aryl, heterocyclyl, C(=Y)R 6 , C(=Y)NR 6 R 7 Selected from the group consisting of C1-C6 alkyl groups substituted with 1-3 substituents (preferably 1) selected from the group consisting of oxyranyl and glycidyl, and therefore, two or fewer of R11, R12 and R13 are H (preferably, one or fewer of R11, R12 and R13 are H), Y is NR 8 Or O (preferably O), R 5R is an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an aryloxy group, or a heterocyclyloxy group. 6 and R 7 is independently H or an alkyl group with 1 to 20 carbon atoms, or R 6 and R 7 These bond to each other to form a 3-6 membered ring by creating an alkylene group of 2-5 carbon atoms, R 8 These are H, linear or branched C1-C20 alkyl and aryl groups. "Polyacrylate" refers to polyacrylates derived from acrylate monomers (ATRPs). The method according to Embodiment 1. 3. The method according to Embodiment 1 or 2, wherein each R1 is independently a C1-C30, C1-C10, or C1-C8 alkyl group, which is linear, branched, or cyclic. 4. The method according to any one of Embodiments 1 to 3, wherein each R is independently a C1-C30 hydrocarbyl group. 5. The method according to Embodiment 4, wherein each R is independently a linear, branched, or cyclic C1-C26, C1-C10, or C1-C8 alkyl group. 6. The method according to any one of Embodiments 1 to 3, wherein each R is independently a polyolefin group. 7. The method according to Embodiment 6, wherein the polyolefin group is an ethylene-based polymeryl group. 8. The method according to Embodiment 7, wherein the polyolefinic group is an ethylene homopolymeric group containing units derived from ethylene. 9. The method according to Embodiment 7, wherein the polyolefin group is an ethylene / alpha-olefin interpolymeryl group containing units derived from ethylene and C3-C30 alpha-olefins. 10. The method according to Embodiment 7, wherein the polyolefin group is an ethylene / alpha-olefin copolymeryl group containing units derived from ethylene and C3-C30 alpha-olefins. 11. The method according to Embodiment 9 or 10, wherein the C3-C30 alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene. 12. The method according to Embodiment 7, wherein the polyolefin group is an ethylene / alpha-olefin multiblock interpolymeryl group. 13. The method according to Embodiment 6, wherein the polyolefin group is selected from the group consisting of block complexes, specific block complexes, and polymeric groups of crystalline block complexes. 14. The method according to Embodiment 6, wherein the polyolefin group is a propylene-based polymeryl group. 15. The method according to Embodiment 14, wherein the polyolefin group is a propylene homopolymeryl group containing a unit derived from propylene. 16. A propylene / alpha-olefin intermediate in which the polyolefin group contains units derived from propylene and ethylene or C4-C30 alpha-olefins. 17. The method according to Embodiment 14, wherein the polyolefin group is a propylene / alpha-olefin copolymeryl group containing units derived from propylene and ethylene or C4-C30 alpha-olefins. 18. The method according to Embodiment 16 or 17, wherein the C4-C30 alpha-olefin is selected from the group consisting of 1-butene, 1-hexene, and 1-octene. 19. The method according to any one of Embodiments 6 to 18, wherein the polyolefinic group can be defined by the properties of RH, and RH has a number average molecular weight greater than 365 g / mol. 20. The method according to any one of Embodiments 6 to 19, wherein the polyolefin group can be defined by the properties of RH, and RH has a number average molecular weight of 365 g / mol to more than 10,000,000 g / mol, or 365 g / mol to more than 5,000,000 g / mol, or 365 g / mol to more than 1,000,000 g / mol, or 365 g / mol to more than 750,000 g / mol, or 365 g / mol to more than 500,000 g / mol, or 365 g / mol to more than 250,000 g / mol. 21. The method according to any one of Embodiments 6 to 20, wherein the polyolefin group can be defined by the properties of RH, and RH has a density of 0.850 to 0.965 g / cc, or 0.860 to 0.950 g / cc, or 0.865 to 0.925 g / cc. 22. The method according to any one of Embodiments 6 to 21, wherein the polyolefin group can be defined by the properties of RH, and RH has a melt index (I2) of 0.01 to 2,000 g / 10 min, or 0.01 to 1,500 g / 10 min, or 0.1 to 1,000 g / 10 min, or 0.1 to 500 g / 10 min, or 0.1 to 100 g / 10 min. 23. The method according to any one of Embodiments 6 to 22, wherein the polyolefin group can be defined by the properties of RH, and RH has a number-average molecular weight distribution (Mw / Mn) of 1 to 10, or 1 to 7, or 1 to 5, or 2 to 4. 24. The method according to any one of embodiments 2 to 23, wherein y is 1 and m is 1. 25. The method according to any one of Embodiments 1 to 24, wherein each of steps a) and b) is performed at a temperature of 40°C to 150°C. 26. The alpha-substituted acrylate is prepared by a method comprising combining a starting material containing alpha-(halomethyl)acrylate with an organometallic compound of formula R2Zn or R3Al, wherein the alpha-(halomethyl)acrylate is of formula (I): [ka] [In the formula, The method according to any one of Embodiments 1 to 25, wherein X is a halide and R and R1 are as defined above. 27. The method according to any one of Embodiments 1 to 26, wherein the transition metal compound is a transition metal halide, and the ligand is an N-, O-, P-, or S-containing ligand that coordinates to the transition metal compound by a sigma bond or a pi bond, or any C-containing compound that can coordinate to the transition metal compound by a pi bond. 28. The method according to any one of Embodiments 1 to 27, wherein the ATRP material and / or reaction material further comprises a solvent. 29. Equation (VI): [ka] [In the formula, "Polyacrylate" is This refers to polyacrylates resulting from atom transfer radical polymerization (ATRP) of acrylate monomers. R1 is hydrogen or a C1-C30 hydrocarbyl group. R is a C1-C26 hydrocarbyl group or a polyolefinyl group. m is between 1 and 50. y is between 1 and 100. X is a halide (preferably Cl, Br, or I), OR 10 , SR 14 ,SeR 14 -SCN (thiocyanate), OC (=O)R 14 , OP(=O)R 14 , OP(=O)(OR 14 )2, OP(=O)OR 14 , ON(R 14 )2, and SC(=S)N(R 14 Selected from the group consisting of )2, R 14 is an aryl or linear or branched C1-C20 (preferably C1-C10) alkyl group, or N(R 14 )When two units exist, two R 14 The groups can bond to form 5-membered, 6-membered, or 7-membered heterocycles, R 10 An olefin-acrylate block copolymer having an alkyl group of 1 to 20 carbon atoms, where each of the hydrogen atoms can be independently substituted with a halide. 30. The olefin-acrylate block copolymer according to Embodiment 29, wherein each R1 is independently a linear, branched, or cyclic C1-C30, C1-C10, or C1-C8 alkyl group. 31. The olefin-acrylate block copolymer according to Embodiment 29 or 30, wherein R is a C1-C26 hydrocarbyl group. 32. The olefin-acrylate block copolymer according to Embodiment 31, wherein R is a linear, branched, or cyclic C1-C26, C1-C10, or C1-C8 alkyl group. 33. The olefin-acrylate block copolymer according to Embodiment 29 or 30, wherein R is a polyolefin group. 34. The olefin-acrylate block copolymer according to Embodiment 33, wherein the polyolefin group is an ethylene-based polymeric group. 35. The olefin-acrylate block copolymer according to Embodiment 34, wherein the polyolefin group is an ethylene homopolymeric group containing units derived from ethylene. 36. The olefin-acrylate block copolymer according to Embodiment 34, wherein the polyolefin group is an ethylene / alpha-olefin interpolymeryl group containing units derived from ethylene and C3-C30 alpha-olefins. 37. The olefin-acrylate block copolymer according to Embodiment 34, wherein the polyolefin group is an ethylene / alpha-olefin copolymeryl group containing units derived from ethylene and C3-C30 alpha-olefins. 38. An olefin-acrylate block copolymer of Embodiment 36 or 37, wherein the C3-C30 alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene. 39. The olefin-acrylate block copolymer according to Embodiment 34, wherein the polyolefin group is an ethylene / alphaolefin multiblock interpolymeryl group. 40. The olefin-acrylate block copolymer according to Embodiment 33, wherein the polyolefinyl group is selected from the group consisting of block complexes, specific block complexes, and polymeric groups of crystalline block complexes. 41. The olefin-acrylate block copolymer according to Embodiment 33, wherein the polyolefin group is a propylene-based polymeryl group. 42. The olefin-acrylate block copolymer according to Embodiment 41, wherein the polyolefin group is a propylene homopolymeric group containing a unit derived from propylene. 43. The olefin-acrylate block copolymer according to Embodiment 41, wherein the polyolefin group is a propylene / alpha-olefin interpolymeryl group containing units derived from propylene and ethylene or C4-C30 alpha-olefins. 44. The olefin-acrylate block copolymer according to Embodiment 41, wherein the polyolefin group is a propylene / alphaolefin copolymeryl group containing units derived from propylene and ethylene or C4-C30 alpha-olefins. 45. An olefin-acrylate block copolymer of Embodiment 43 or 44, wherein the C4-C30 alpha-olefin is selected from the group consisting of 1-butene, 1-hexene, and 1-octene. 46. ​​The olefin-acrylate block copolymer according to any one of Embodiments 33 to 45, wherein the polyolefin group can be defined by the properties of RH, and RH has a number-average molecular weight greater than 365 g / mol. 47. The olefin-acrylate block copolymer according to any one of Embodiments 33 to 46, wherein the polyolefin group can be defined by the properties of RH, and RH has a number average molecular weight of 365 g / mol to more than 10,000,000 g / mol, or 365 g / mol to more than 5,000,000 g / mol, or 365 g / mol to more than 1,000,000 g / mol, or 365 g / mol to more than 750,000 g / mol, or 365 g / mol to more than 500,000 g / mol, or 365 g / mol to more than 250,000 g / mol. 48. The polyolefin group can be defined by the properties of RH, where RH has a density of 0.850-0.965 g / cc, or 0.860-0.950 g / cc, or 0.865-0.925 g / cc. The olefin-acrylate block copolymer according to any one of embodiments 33 to 47, wherein the polyolefin group can be defined by the properties of RH, and RH has a melt index (I2) of 0.01 to 2,000 g / 10 min, or 0.01 to 1,500 g / 10 min, or 0.1 to 1,000 g / 10 min, or 0.1 to 500 g / 10 min, or 0.1 to 100 g / 10 min. 49. An olefin-acrylate block copolymer according to any one of embodiments 33 to 48, wherein the polyolefin group can be defined by the properties of RH, and RH has a number-average molecular weight distribution (Mw / Mn) of 1 to 10, or 1 to 7, or 1 to 5, or 2 to 4. 50. An olefin-acrylate block copolymer according to any one of embodiments 33 to 49, wherein y is 1 and m is 1. 51. The acrylate monomer is of formula (III): [ka] An olefin-acrylate block copolymer according to any one of embodiments 33 to 50, having [wherein R1 is hydrogen or a C1-C30 hydrocarbyl group, and R2 is hydrogen or a methyl group].

[0073] Test method density: The density is measured according to Method B of ASTM D-792.

[0074] Melt Index: The melt index (I2) was measured according to ASTM D-1238, conditions 190°C / 2.16 kg, which is incorporated herein by reference in its entirety, and reported as grams eluted per 10 minutes.

[0075] GPC The properties of the sample polymers were tested via GPC according to the following procedure.

[0076] A high-temperature gel permeation chromatography (GPC IR) system consisting of an infrared concentration detector (IR-5) from PolymerChar Inc (Valencia, Spain) was used to determine molecular weight (MW) and molecular weight distribution (MWD). The support solvent was 1,2,4-trichlorobenzene (TCB). The autosampler compartment was operated at 160°C, and the column compartment at 150°C. The columns used were four Polymer Laboratories Mixed A LS, 20 micron columns. The chromatography solvent (TCB) and sample preparation solvent were from the same solvent source, which was sprayed with 250 ppm butylated hydroxytoluene (BHT) and nitrogen. Samples were prepared in TCB at a concentration of 2 mg / mL. Polymer samples were gently shaken at 160°C for 2 hours. The injection volume was 200 μL, and the flow rate was 1.0 ml / min.

[0077] The GPC column set was calibrated using 21 polystyrene standards with narrow molecular weight distributions. The molecular weights of the standards ranged from 580 to 8,400,000 g / mol and were arranged in six "cocktail" mixtures, with at least an order of magnitude of separation between individual molecular weights.

[0078] Prior to performing the examples, the GPC column set was calibrated by running 21 polystyrene standards with narrow molecular weight distributions. The molecular weights (Mw) of the standards ranged from 580–8,400,000 grams per mole (g / mol), and the standards were contained in six “cocktail” mixtures. Each standard mixture had at least an order of magnitude of spacing between individual molecular weights. The standard mixtures were purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards were prepared at 0.025 g in 50 mL of solvent for molecular weights of 1,000,000 g / mol or more, and 0.05 g in 50 mL of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards were dissolved at 80°C with gentle stirring for 30 minutes. The narrow standard mixtures were run first, and in an order decreasing the highest molecular weight (Mw) component to minimize degradation. The peak molecular weights of the polystyrene standards were converted to polyethylene Mw using the Mark-Houwink constant. Once the constants were obtained, the two values ​​were used to construct two linear reference normal calibrations for polyethylene molecular weight and polyethylene intrinsic viscosity as functions of the elution column.

[0079] The standard peak molecular weight of polystyrene was converted to the molecular weight of polyethylene using the following formula (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)). M ポリエチレン =A(M ポリスチレン ) B (1)

[0080] In the equation, B has a value of 1.0, and the experimentally determined value of A is approximately 0.41.

[0081] A cubic polynomial was used, and the respective polyethylene equivalent calibration points obtained from equation (1) were fitted to the elution deposition of their observed polystyrene standards.

[0082] The number-average, weight-average, and z-average molecular weights were calculated according to the following formulas.

number

[0083] In the formula, Wf i This is the weight fraction of the i-th component, and M i is the molecular weight of the i-th component.

[0084] MWD was expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn).

[0085] The precise A value was determined by adjusting the A value in equation (1) until the Mw and corresponding retention / deposition polynomial calculated using equation (3) matched the known Mw value of 120,000 g / mol for the standard linear polyethylene homopolymer reference.

[0086] The GPC system consists of a Waters (Milford, Mass.) 150°C high-temperature chromatograph equipped with an onboard differential refractive index detector (RI) (other suitable high-temperature GPC equipment includes Polymer Laboratories (Shropshire, UK) Model 210 and Model 220). Additional detectors may include a Polymer ChAR (Valencia, Spain) IR4 infrared detector, a Precision Detectors (Amherst, Mass.) 2-angle laser light scattering detector Model 2040, and a Viscotek (Houston, Tex.) 150R 4-capillary solution viscometer. A GPC having the last two independent detectors and at least one of the initial detectors is sometimes referred to as a "3D-GPC," although the term "GPC" alone generally refers to a conventional GPC. Depending on the sample, either a 15-degree or 90-degree angle of the light scattering detector was used for calculation purposes.

[0087] Data acquisition was performed using Viscotek TriSEC software, version 3, and a four-channel Viscotek Data Manager DM400. This system also included an online solvent degasser from Polymer Laboratories (Shropshire, UK). Suitable high-temperature GPC (MixA LS, Polymer Lab) columns could be used, such as four 30cm Shodex HT803 13-micron columns or a 30cm Polymer Lab column with four 20-micron mixed pore size packings. The sample carousel compartment was operated at 140°C, and the column compartment at 150°C. Samples were prepared at a polymer concentration of 0.1 grams in 50 ml of solvent. Both the chromatographic solvent and sample preparation solvent contained 200 ppm butylated hydroxytoluene (BHT). Nitrogen was sprayed into both solvents. The polyethylene samples were gently stirred at 160°C for 4 hours (4 hours). The injection volume was 200 microliters (μL). The flow rate through the GPC was set to 1 ml / min.

[0088] NMR ( 13 C and 1 H): NMR analysis was performed at room temperature using standard NMR solvents such as chloroform or benzene, and the data was acquired using a Varian 500 MHz spectrometer.

[0089] Diffusion NMR: The experiment employed 2048 scans and a repetition time of 15 seconds. The spectrum was centered at 90 ppm and covered a bandwidth of 240 ppm. The self-diffusion coefficient (D) was measured by diffusion detected at 1H and 13C using pulsed-field gradient NMR with dual-stimulation echoes, mitigating any artifacts due to thermal convection. In general, this method utilizes the spatial variation of the magnetic field, i.e., the magnetic field gradient (g), to physically label the spatial position of a molecular ensemble over a clearly defined time interval, thereby coupling the NMR peak intensity to the self-diffusion (D) of each molecule. D is quantified using the Stejskal-Tanner equation (Eq. 5) [wherein I and I0 represent NMR signal intensity with or without gradient], where γ is the gyromagnetic ratio of the nucleus, g is the gradient intensity, δ is the gradient pulse duration, and Δ is the diffusion time. Keeping in mind that peaks from the same molecule must yield the same D, such a method allows for the intrinsic separation of NMR peaks by the D associated with each peak without perturbing the spectral resolution. This method can also be considered essentially an analogue of size exclusion chromatography (SEC), meaning that large molecules are either delayed / eluted early or vice versa. Therefore, the measurement is D end and D backbone By comparing these, clear intermolecular information is provided to determine whether the polymer backbone is capped by specific end groups.

number

[0090] GCMS: Tandem gas chromatography / low-resolution mass spectrometry using electron impulse ionization (EI) is performed at 70 eV on an Agilent Technologies 6890N series gas chromatograph equipped with an Agilent Technologies 5975 inert XL mass-selective detector and an Agilent Technologies Capillary column (HP1MS, 15 m × 0.25 mm, 0.25 micron) for the following: Programmed method: Oven equilibration time: 0.5 minutes at 50°C Next, heat up to 200°C at 25°C / min, and hold for 5 minutes. Execution time: 11 minutes [Examples]

[0091] The following embodiments are intended to illustrate some embodiments of the present invention and should not be construed as limiting the scope of the invention as described in the claims.

[0092] Unless otherwise specified, all materials and reagents are commercially available from, for example, Sigma-Aldrich. Example 1 [ka]

[0093] The reaction of Example 1 was carried out under an inert nitrogen atmosphere glove box according to the exemplary and non-limiting reaction scheme described above. 5.88 mL of 0.30 M zinc dioctyl solution in Isopar® E (1.76 mmol) was added to a 20 mL vial. The solution was heated to 60°C. 0.500 g of methyl 2-(chloromethyl) acrylate (3.72 mmol, 2 equivalents) was added dropwise to the hot zinc dioctyl solution. During the slow addition, the solution changed from pale brown to clear and became cloudy with a visible white precipitate. After several minutes, the precipitate settled at the bottom of the vial as a sticky yellow residue. After 48 hours at 60°C, 83 mg of hexamethylbenzene (0.511 mmol) was added as an internal NMR standard. The NMR conversion rate was calculated to be 62.6%. The NMR analysis is shown in Figures 1A and 1B. As shown in Figures 1C and 1D, GC-MS of the reaction aliquots showed the formation of the desired product (the lower retention time peak corresponds to Isopar® E). The reaction mixture was quenched with water. Purification to remove the Zn salt and internal standard was performed by column chromatography eluting with a hexane mixture of 2% ethyl acetate. 405 mg of the product was isolated (51%). Example 2 [ka]

[0094] The reaction was carried out in a nitrogen-atmosphere glove box according to the ATRP procedure described in Macromolecules vol 33, 4039-4047, 2000. Before the reaction began, t-BA was passed through an alumina cartridge to remove the inhibitor. CuBr (78.2 mg, 0.545 mmol), CuBr2 (6.0 mg, 0.027 mmol), and 1,3,5-trimethoxybenzene (9 mg, 0.054 mmol) were added to a dry 20 mL vial. After adding deoxygenated acetone (1 mL), t-BA (4.0 mL, 27.6 mmol) was added. PMDETA (120 μL, 0.575 mmol) was added, and the solution was stirred for about 20 minutes until the Cu complex was formed. After complex formation, methyl 2-bromopropionate (121 μL, 1.09 mmol) was added to the flask, the initial sample was removed, and the vial was heated to 55°C. An increase in viscosity indicating polymerization had occurred was observed. After the majority of the monomers had reacted, as determined by NMR, methyl 2-methylene undecanoate (0.232 g, 1.09 mmol) was added, and the reaction mixture was stirred overnight at 55°C.

[0095] NMR (as seen in Figures 2A and 2B) confirmed that all compounds prepared in Example 1 had reacted overnight. Approximately 10 mL of THF was added to the vial to dissolve the polymer, and the reaction mixture was passed through an alumina column to remove the copper catalyst. Attempts to crush the polymer in cold hexane were unsuccessful. The solvent was removed using a rotary evaporator to obtain a viscous yellow polymer. The polymer was washed with chlorobenzene to remove excess hexane and THF, and dried overnight under vacuum at 70°C.

[0096] According to GPC: Mw=3726, Mn=3125, and PDI=1.19. Example 3 [ka]

[0097] The reaction was carried out in a nitrogen-atmosphere glove box according to the ATRP procedure described in Macromolecules vol 33, 4039-4047, 2000. Before starting the reaction, t-BA was passed through an alumina cartridge to remove the inhibitor. CuBr (78.2 mg, 0.545 mmol) and CuBr2 (6.0 mg, 0.027 mmol) were added to a dry 20 mL vial. Deoxygenated acetone (1 mL) was added, followed by t-BA (4.0 mL, 27.6 mmol). PMDETA (120 μL, 0.575 mmol) was added, and the solution was stirred for approximately 20 minutes until the Cu complex was formed. After complex formation, methyl 2-bromopropionate (61 μL, 0.547 mmol) was added to the flask, the initial sample was removed, and the vial was heated to 60°C. After 3 hours, before all monomers had reacted, THF was added to the reaction mixture, and the reaction was stopped by passing the solution through an alumina plug to remove the Cu catalyst. The THF was removed using a rotary evaporator, followed by drying at 70°C over the weekend on a Schlenklein to remove most of the THF. The dried polymer was a pink solid (2.18 g). The flask was returned to the glove box, and 10 mL of degassed acetone was added. A 0.044 M solution of poly(t-butyl acrylate) was used in the next step.

[0098] CuBr (0.015 g, 0.1046 mmol), methyl 2-methylene undecanoate (0.026 g, 0.122 mmol), and 1 mL of degassed acetone were added to a 20 mL vial equipped with a stirring bar. PMDETA (0.023 mL, 0.110 mmol) was added, and the mixture was stirred for 20 minutes. 2.37 mL of poly(t-butyl acrylate) macroinitiator solution was injected into the reaction vial from a syringe. The initial sample was removed, and the reaction was stirred at 55°C. After reacting overnight, the NMR showed approximately 30% conversion. The acetone solvent was partially removed with nitrogen to increase the concentration of the reactants.

[0099] After 36 hours, the vial was removed from the heating block, approximately 20 mL of THF was added, and the reaction was stopped by passing the solution through an alumina plug to remove the copper catalyst. Attempts to crush the polymer in cold hexane were unsuccessful. The solution was dried in a rotary evaporator, washed with chlorobenzene to remove excess hexane and THF, and dried overnight under vacuum at 70°C.

[0100] The NMR spectra of Example 3 are shown in Figures 3A and 3B.

[0101] GPC results: Mw=6906, Mn=5795, and PDI=1.19. 1H NMR results: Mn=5250. The invention described in the original claims of this application is listed below. [1] A method for preparing an olefin-acrylate block copolymer, a) Performing atomic transfer radical polymerization (ATRP) by combining an acrylate monomer, an initiator having radical-transferable atoms or groups, a transition metal compound, and a ligand, thereby forming a macroinitiator, b) Combining a reaction material containing an alpha-substituted acrylate and the macroinitiator, thereby forming the olefin-acrylate block copolymer, Methods that include... [2] The alpha-substituted acrylate has formula (II), [ka] The acrylate monomer has formula (III), [ka] The initiator has formula (IV), [ka] The macroinitiator has formula (V), Polyacrylate-(X) y (V) The olefin-acrylate block copolymer has formula (VI), [ka] During the ceremony, Each R1 is independently either hydrogen or a C1-C30 hydrocarbyl group. Each R2 is independently either a hydrogen atom or a methyl group. Each R is independently a C1-C26 hydrocarbyl group or a polyolefinyl group. m is between 1 and 50. Each y is independently between 1 and 100. Each X is independently a halide, OR 10 , SR 14 ,SeR 14 -SCN (thiocyanate), OC (=O)R 14 , OP(=O)R 14 , OP(=O)(OR 14 ) 2 , OP(=O)OR 14 , ON(R 14 ) 2 , and SC(=S)N(R 14 ) 2 Selected from the group consisting of R 14 is an aryl or linear or branched C1-C20 alkyl group, or N(R 14 ) 2 When the group exists, the two R 14 The groups can bond to form 5-membered, 6-membered, or 7-membered heterocycles, R 10 This is an alkyl group with 1 to 20 carbon atoms, and each of the hydrogen atoms may be independently substituted with a halide. R11, R12, and R13 are each independently H, halide, C1-C20 alkyl, C3-C8 cycloalkyl, and C(=Y)R. 5 , C(=Y)NR 6 R 7 COCl, OH, CN, C2-C20 alkenyl or alkynyl, oxyranyl, glycidyl, aryl, heterocyclyl, aralkyl, aralkylene (aryl-substituted alkenyls, and alkenyls are vinyls that can be substituted with one or two C1-C6 alkyl and / or halogen atoms, preferably chlorine), C1-C6 alkyls in which one to all hydrogen atoms are substituted with halogens, and C1-C4 alkoxy, aryl, heterocyclyl, C(=Y)R 6 , C(=Y)NR 6 R 7 The group consists of C1-C6 alkyl groups substituted with 1-3 substituents selected from the group consisting of oxyranyl and glycidyl, and therefore, two or fewer of R11, R12, and R13 are H. Y is NR 8 or O, R 5 R is an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an aryloxy group, or a heterocyclyloxy group. 6 and R 7 is independently H or an alkyl group with 1 to 20 carbon atoms, or R 6 and R 7 These bond to each other to form a 3-6 membered ring by creating an alkylene group of 2-5 carbon atoms, R 8 These are H, linear or branched C1-C20 alkyl and aryl groups. "Polyacrylate" refers to the polyacrylate derived from the ATRP of the acrylate monomer. The method described in [1]. [3] The method according to [2], wherein each R is independently a C1-C26 hydrocarbyl group. [4] The method according to [2], wherein each R is independently a polyolefin group. [5] The method according to [4], wherein the polyolefinyl group is an ethylene-based polymeryl group. [6] The method according to [4], wherein the polyolefinyl group is a propylene-based polymeryl group. [7] The method according to any one of [4] to [6], wherein the polyolefin group can be defined by the properties of RH, and RH has a number average molecular weight greater than 365 g / mol. [8] The method according to any one of [1] to [7], wherein each of steps a) and b) is performed at a temperature of 40°C to 150°C. An olefin acrylate block copolymer prepared by any of the methods described in [9] [1] to [8].

[10] Equation (VI):

change

Claims

1. A method for preparing olefin-acrylate block copolymers, a) Performing atomic transfer radical polymerization (ATRP) by combining an acrylate monomer, an initiator having radical-transferable atoms or groups, a transition metal compound, and a ligand, thereby forming a macroinitiator, b) Combining a reaction material containing an alpha-substituted acrylate and the macroinitiator, thereby forming the olefin-acrylate block copolymer, A method including, The alpha-substituted acrylate has formula (II), 【Chemistry 1】 The olefin-acrylate block copolymer has formula (VI), 【Chemistry 2】 During the ceremony, Each R1 is independently a C1-C30 hydrocarbyl group. Each R is independently a C1-C26 hydrocarbyl group or a polyolefinyl group. m is 1, y is 1, Each X is independently a halide, OR １０ , SR １４ , SeR １４ , -SCN (thiocyanate), OC(=O)R １４ , OP(=O)R １４ , OP(=O)(OR １４ ) ２ , OP(=O)OR １４ , O-N(R １４ ) ２ , and S-C(=S)N(R １４ ) ２ selected from the group consisting of, R １４ is an aryl or a linear or branched C1-C20 alkyl group, or when the N(R １４ ) ２ group is present, the two R １４ groups can combine to form a 5-, 6- or 7-membered heterocycle, R １０ is alkyl of 1 to 20 carbon atoms, each of the hydrogen atoms thereof may be independently substituted with a halide, "Polyacrylate" refers to the polyacrylate derived from the ATRP of the acrylate monomer. method.

2. The acrylate monomer has formula (III), 【Transformation 3】 The initiator has formula (IV), 【Chemistry 4】 The macroinitiator has formula (V), Polyacrylate-(X) ｙ (V) Each R1 is independently a C1-C30 hydrocarbyl group. Each R2 is a hydrogen atom. y is 1, Each X is independently halide, OR １０ , SR １４ ,SeR １４ ,-SCN (thiocyanate), OC (=O)R １４ , OP(=O)R １４ ,OP(=O)(OR １４ ) ２ , OP (=O) OR １４ , O-N (R １４ ) ２ , and S-C(=S)N(R １４ ) ２ Selected from the group consisting of R １４ is an aryl or linear or branched C1-C20 alkyl group, or N(R １４ ) ２ When the group exists, the two R １４ The groups can bond to form a 5-membered, 6-membered, or 7-membered heteroring, R １０ This is an alkyl group with 1 to 20 carbon atoms, and each of the hydrogen atoms may be independently substituted with a halide. R11, R12, and R13 are each independently H, halide, C1-C20 alkyl, C3-C8 cycloalkyl, and C(=Y)R. ５ , C(=Y)NR ６ R ７ COCl, OH, CN, C2-C20 alkenyl or alkynyl, oxyranyl, glycidyl, aryl, heterocyclyl, aralkyl, aralkylene, C1-C6 alkyl in which one to all hydrogen atoms are substituted with halogens, and C1-C4 alkoxy, aryl, heterocyclyl, C(=Y)R ６ , C(=Y)NR ６ R ７ Selected from the group consisting of C1-C6 alkyl groups substituted with 1-3 substituents selected from the group consisting of oxyranyl and glycidyl, and therefore, two or fewer of R11, R12 and R13 are H, Y is NR ８ or O, R ５ R is an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an aryloxy group, or a heterocyclyloxy group. ６ and R ７ is independently H or an alkyl group with 1 to 20 carbon atoms, or R ６ and R ７ These bond to each other to form a 3-6 membered ring by creating an alkylene group of 2-5 carbon atoms, R ８ These are H, linear or branched C1-C20 alkyl and aryl atoms. The method according to claim 1.

3. The method according to claim 2, wherein each R is independently a C1-C26 hydrocarbyl group.

4. The method according to claim 2, wherein each R is independently a polyolefin group.

5. The method according to claim 4, wherein the polyolefinyl group is an ethylene-based polymeryl group.

6. The method according to claim 4, wherein the polyolefin group is a propylene-based polymeryl group.

7. The method according to any one of claims 4 to 6, wherein the polyolefinic group can be defined by the properties of R-H, and R-H has a number average molecular weight greater than 365 g / mol.

8. The method according to any one of claims 1 to 7, wherein each of steps a) and b) is performed at a temperature of 40°C to 150°C.

9. Equation (VI): 【Transformation 5】 [In the formula, "Polyacrylate" is This refers to polyacrylates resulting from atom transfer radical polymerization (ATRP) of acrylate monomers. R1 is independently a C1-C30 hydrocarbyl group. Each R is independently a C1-C26 hydrocarbyl group or a polyolefinyl group. m is 1, y is 1, Each X is independently halide, OR １０ , SR １４ ,SeR １４ ,-SCN (thiocyanate), OC (=O)R １４ , OP(=O)R １４ ,OP(=O)(OR １４ ) ２ , OP (=O) OR １４ , O-N (R １４ ) ２ , and S-C(=S)N(R １４ ) ２ Selected from the group consisting of R １４ is an aryl or linear or branched C1-C20 alkyl group, or N(R １４ ) ２ When the group exists, the two R １４ The groups can bond to form a 5-membered, 6-membered, or 7-membered heteroring, R １０ An olefin-acrylate block copolymer having an alkyl group of 1 to 20 carbon atoms, where each of the hydrogen atoms can be independently substituted with a halide.

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