Process for the preparation of olefin-acrylate block copolymers by ATRP

Abstract

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

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 018272, filed April 30, 2020, which is incorporated herein by reference in its entirety. Background Technology

[0003] 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, which are then reacted with α-substituted acrylate monomers (such as α-(alkyl)acrylate monomers or α-(polymer-based)acrylate monomers). During this method, α-substituted acrylate monomers suitable for reaction using standard ATRP methods known in the art are used as monomers to react with the polyacrylates prepared by ATRP to form olefin-acrylate block copolymers. This method and the resulting olefin-acrylate block copolymers were not achieved until the disclosure of this application. Summary of the Invention

[0004] This disclosure relates to a method for preparing olefin-acrylate block copolymers, the method comprising:

[0005] a) ATRP is performed by combining materials containing acrylate monomers, initiators with radical-transferable atoms or groups, transition metal compounds, and ligands to form macromolecular initiators; and

[0006] b) Combining reactive materials comprising α-substituted acrylates and the macromolecular initiator to form the olefin-acrylate block copolymer.

[0007] This disclosure also relates to olefin-acrylate block copolymers prepared by the method of the present invention. Attached Figure Description

[0008] Figure 1A and Figure 1B Each of the following is provided in Example 1 1 H NMR and 13 C NMR spectrum.

[0009] Figure 1C and Figure 1D The GCMS spectrum of Example 1 is provided.

[0010] Figure 2A and Figure 2B Provided respectively Example 2 1 1H NMR and diffused NMR spectra.

[0011] Figure 3A and Figure 3B Provided respectively Example 3 1 1H NMR and diffused NMR spectra. Detailed Implementation

[0012] definition

[0013] All references to the periodic table in this document refer to the periodic table published and copyrighted by CRC Press, Inc. in 2003. Furthermore, any reference to one or more groups refers to one or more groups reflected in such a periodic table that uses the IUPAC system for group numbering.

[0014] Unless otherwise stated, implied by the context or customary in the art, all parts and percentages are by weight.

[0015] For the purposes of U.S. patent practice, any patent, patent application or publication mentioned herein is hereby incorporated in its entirety by reference (or its equivalent U.S. version by reference), especially disclosures concerning synthetic techniques, definitions (in case of any inconsistency with those provided herein) and common knowledge in the art.

[0016] The numerical ranges disclosed herein encompass all values ​​from the lower limit to the upper limit, and include both the lower and upper limits. For ranges containing exact values ​​(e.g., 1 or 2; or 3 to 5; or 6; or 7), any subranges between any two exact values ​​are included (e.g., 1 to 2 → 2 to 6; 5 to 7; 3 to 7; 5 to 6, etc.). The numerical ranges disclosed herein further include fractions between any two exact values.

[0017] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not specifically disclosed. Conversely, the term "consisting of" excludes any other component, step, or procedure from any subsequently listed scope, except those that are not essential for operability. The term "consisting of" excludes any component, step, or procedure not specifically described or listed. Unless otherwise stated, the term "or" refers to members listed individually and in any combination.

[0018] As used herein, the terms "hydrocarbyl", "hydrocarbyl group", and similar terms refer to compounds consisting entirely of hydrogen and carbon, including aliphatic, aromatic, acyclic, cyclic, polycyclic, branched, unbranched, saturated, and unsaturated compounds. The terms "hydrocarbyl", "hydrocarbyl group", "alkyl", "alkylgroup", "aryl", "aryl group", and similar terms are intended to encompass every possible isomer, including every structural or stereoisomer.

[0019] The term "cyclic" refers to a series of atoms in a polymer or compound, wherein such a series comprises one or more rings. Therefore, the term "cyclic hydrocarbon group" refers to a hydrocarbon group containing one or more rings. As used herein, a "cyclic hydrocarbon group" may contain an acyclic (straight-chain or branched) portion in addition to one or more rings.

[0020] The term "polymer" refers to a compound prepared by reacting (i.e., polymerizing) a group of monomers, wherein the group of monomers is a homogeneous (i.e., only one type) group of monomers or a heterogeneous (i.e., more than one type) group of monomers. As used herein, the term polymer includes the term "homogeneous polymer," which means a polymer prepared from a homogeneous group of monomers, and the term "interpolymer" as defined below.

[0021] "Interpolymer" refers to polymer A prepared by polymerizing at least two different types of monomers. This term includes "copolymer," which is a polymer prepared from two different types of monomers, as well as polymers prepared from more than two different types of monomers, such as terpolymers, tetrpolymers, etc. This term also includes all forms of interpolymers, such as random, block, homogeneous, and heterogeneous polymers.

[0022] "Polyolefin" is a polymer produced by polymerizing olefins as monomers, wherein the olefin monomers are straight-chain, branched, or cyclic compounds having at least one double bond of carbon and hydrogen. Therefore, as used herein, the term "polyolefin" includes and encompasses the terms "vinyl polymer," "propylene polymer," "ethylene homopolymer," "propylene homopolymer," "ethylene / α-olefin interpolymer," "ethylene / α-olefin copolymer," "ethylene / α-olefin multiblock interpolymer," "block complex," "specified block complex," "crystalline block complex," and "propylene / α-olefin interpolymer" and "propylene / α-olefin copolymer."

[0023] "Vinyl polymer" is a polymer containing, by weight of the polymer, a majority amount of polymerized ethylene and optionally, polymeric units containing at least one comonomer. "Vinyl interpolymer" is an interpolymer containing, by weight of the interpolymer, a majority amount of ethylene in polymeric form and optionally, polymeric units containing at least one comonomer. "Ethylene homopolymer" is a polymer comprising repeating units derived from ethylene, but excluding residual amounts of other components.

[0024] As used herein, the term "ethylene / α-olefin interpolymer" refers to a polymer comprising a substantial weight percentage of ethylene (by weight of the interpolymer) in polymeric form and at least one comonomer as an α-olefin. Ethylene / α-olefin interpolymers can be random or block interpolymers. The term "ethylene / α-olefin interpolymer" encompasses the terms "ethylene / α-olefin copolymer" and "ethylene / α-olefin multiblock interpolymer".

[0025] As used herein, the term "ethylene / α-olefin copolymer" refers to a copolymer comprising a majority weight percentage of ethylene (by weight of the copolymer) in polymeric form and a comonomer as an α-olefin, wherein ethylene and α-olefin are the only two monomer types. Ethylene / α-olefin copolymers can be random or block copolymers.

[0026] As used herein, the term "ethylene / α-olefin multiblock interpolymer" or "olefin block copolymer" refers to an interpolymer comprising ethylene and one or more copolymerizable α-olefin comonomers in polymerizable form, characterized by multiple blocks or segments of two or more (preferably three or more) polymeric monomer units that are chemically or physically distinct. Specifically, the term refers to a polymer comprising two or more (preferably three or more) chemically distinct regions or segments (referred to as "blocks") joined in a linear rather than overhanging or grafting manner, i.e., a polymer comprising chemically distinct units joined end-to-end (covalently bonded) relative to polymeric functional groups. The difference between block copolymers lies in the amount or type of comonomers incorporated, density, amount of crystallinity, type of crystallinity (e.g., polyethylene versus polypropylene), crystallite size of the polymer attributable to this composition, type or degree of stereoregularity (isosteryl or syndiotactic), regional regularity or regional irregularity, amount of branching (including long-chain branching or hyperbranching), homogeneity, and / or any other chemical or physical properties. Block copolymers are characterized by a unique distribution of both polymer polydispersity (PDI or Mw / Mn) and block length distribution, for example, based on the effect of using one or more shuttle agents in combination with a catalyst system. Non-limiting examples of olefin block copolymers disclosed herein and methods for preparing them are disclosed in U.S. Patent Nos. 7,858,706B2, 8,198,374B2, 8,318,864B2, 8,609,779B2, 8,710,143B2, 8,785,551B2 and 9,243,090B2, all of which are incorporated herein by reference in their entirety.

[0027] The term "block complex" ("BC") refers to a polymer comprising three polymeric components: (i) a vinyl polymer (EP) with an ethylene content of 10 mol% to 90 mol% based on the total moles of polymeric monomer units in the vinyl polymer (EP) (soft copolymer); (ii) an α-olefin polymer (AOP) with an α-olefin content greater than 90 mol% based on the total moles of polymeric monomer units in the α-olefin polymer (AOP) (hard copolymer); and (iii) a block copolymer having ethylene blocks (EB) and α-olefin blocks (AOB) (diblock copolymer); wherein the ethylene blocks of the block copolymer have the same composition as the EP of component (i) of the block complex, and the α-olefin blocks of the block copolymer have the same composition as the AOP of component (ii) of the block complex. Furthermore, in the block complex, the compositional division between the amounts of EP and AOP will be substantially the same as the compositional division between corresponding blocks in the block copolymer. Non-limiting examples of block complexes disclosed herein, as well as methods for preparing them, are disclosed in U.S. Patent Nos. 8,686,087 and 8,716,400, which are incorporated herein by reference in their entirety.

[0028] The term "specified block complex" ("SBC") refers to a polymer comprising three polymer components: (i) a vinyl polymer (EP) with an ethylene content of 78 mol% to 90 mol% based on the total moles of polymeric monomer units in the vinyl polymer (EP) (soft copolymer); (ii) an α-olefin polymer (AOP) with an α-olefin content of 61 mol% to 90 mol% based on the total moles of polymeric monomer units in the α-olefin polymer (AOP) (hard copolymer); and (iii) a block copolymer having ethylene blocks (EB) and α-olefin blocks (AOB) (diblock copolymer); wherein the ethylene blocks of the block copolymer have the same composition as the EP of component (i) of the specified block complex, and the α-olefin blocks of the block copolymer have the same composition as the AOP of component (ii) of the specified block complex. Furthermore, in the specified block complex, the compositional division between the amounts of EP and AOP will be substantially the same as the compositional division between the corresponding blocks in the block copolymer. Non-limiting examples of specified block complexes of this disclosure and methods for preparing them are disclosed in WO2017 / 044547, which is incorporated herein by reference in its entirety.

[0029] The term "crystalline block complex" ("CBC") refers to a polymer comprising three components: (i) a crystalline vinyl polymer (CEP) with an ethylene content greater than 90 mol% based on the total molar number of polymeric monomer units (CEP) in the crystalline vinyl polymer; (ii) a crystalline α-olefin copolymer (CAOP) with an α-olefin content greater than 90 mol% based on the total molar number of polymeric monomer units in the crystalline α-olefin copolymer (CAOP); and (iii) a block copolymer comprising crystalline ethylene blocks (CEB) and crystalline α-olefin blocks (CAOB); wherein 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. Furthermore, in a crystalline block complex, the compositional division between the amounts of CEP and CAOP will be substantially the same as the compositional division between corresponding blocks in the block copolymer. Non-limiting examples of crystalline block complexes disclosed herein, as well as methods for preparing them, are disclosed in U.S. Patent Nos. 8,822,598B2 and WO 2016 / 01028961 A1, which are incorporated herein by reference in their entirety.

[0030] "Propylene-based polymer" is a polymer containing, by weight of the polymer, a majority amount of polymerized propylene and optionally, polymeric units containing at least one comonomer. "Propylene-based interpolymer" is an interpolymer containing, by weight of the interpolymer, a majority amount of propylene in polymeric form and further containing at least one comonomer. "Propylene homopolymer" is a polymer comprising repeating units derived from propylene, but excluding residual amounts of other components.

[0031] As used herein, the term "propylene / α-olefin interpolymer" refers to a polymer comprising a substantial weight percentage of propylene (by weight of the interpolymer) in polymeric form and at least one comonomer as an α-olefin (wherein ethylene is considered an α-olefin). Propylene / α-olefin interpolymers can be random or block interpolymers. The term "propylene / α-olefin interpolymer" includes the term "propylene / α-olefin copolymer".

[0032] As used herein, the term "propylene / α-olefin copolymer" refers to a copolymer comprising a majority weight percentage of propylene (by weight of the copolymer) in polymeric form and a comonomer as an α-olefin, wherein propylene and α-olefin are the only two monomer types. Propylene / α-olefin copolymers can be random or block copolymers.

[0033] The terms "polymeryl", "polymeryl group" and similar terms refer to polymers that lack one hydrogen atom.

[0034] The terms "polyolefinyl", "polyolefinyl group" and similar terms refer to polyolefins lacking one hydrogen atom.

[0035] Atom transfer radical polymerization (ATRP)

[0036] Step a) of the method disclosed herein relates to the formation of functionalized polyacrylates via ATRP. Specifically, step a) of the method of the present invention relates to ATRP by combining an ATRP material comprising an acrylate monomer, an initiator having radical-transferable atoms or groups, a transition metal compound, and a ligand, thereby forming a macromolecular initiator. The techniques and conditions suitable for ATRP in step a) are known in the art and include, for example, those described in Macromolecules, 33,4039-4047,2000 and U.S. Patent No. 5,945,491, both of which are incorporated herein by reference. In fact, each of the initiators, transition metal compounds, and ligands in the ATRP material is known in the art and is disclosed, for example, in U.S. Patent No. 5,945,491.

[0037] In some embodiments, the acrylate monomer of step a) has formula (III):

[0038]

[0039] R1 is a hydrogen or C1-C30 hydrocarbon group and R2 is a hydrogen or methyl group.

[0040] In some embodiments, R1 may be a straight-chain, branched, or cyclic C1-C30 hydrocarbon group. In other embodiments, R1 may be a straight-chain, branched, or cyclic C1-C30 alkyl group. For example, R1 may be a straight-chain, branched, or cyclic alkyl group comprising 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 8 carbon atoms.

[0041] In some embodiments, the initiator has formula (IV):

[0042] in:

[0043] x is selected from the group consisting of: halide ions (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) OR14 ON(R) 14 )2 and SC(=S)N(R 14 )2, where R 14 It is an aryl or straight-chain or branched C1-C20 (preferably C1-C10) alkyl group, or when N(R 14 When the )2 group is present, the two R groups 14 The groups can connect to form 5, 6, or 7-membered heterocycles, and R... 10 It is an alkyl group with 1 to 20 carbon atoms, wherein each hydrogen atom can be independently replaced by a halide ion;

[0044] R11, R12, and R13 are each independently selected from the group consisting of: H, halide ions, C1-C20 alkyl (preferably C1-C10 alkyl, and 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, and more preferably vinyl), ethylene oxide, glycidyl, aryl, heterocyclic, aralkyl, arylalkylene (aryl-substituted alkenyl, and the alkenyl is a vinyl that can be substituted by one or two C1-C6 alkyl groups and / or halogen atoms, preferably chlorine-substituted), C1-C6 alkyl groups wherein one to all hydrogen atoms (preferably one) are substituted by a halogen (preferably fluorine or chlorine, wherein one or more hydrogen atoms are substituted, and preferably fluorine, chlorine or bromine, wherein one hydrogen atom is substituted) and C1-C6 alkyl groups substituted by one to three C1-C4 alkoxy, aryl, heterocyclic, C(=Y)R 6 C(=Y)NR 6 R 7 The C1-C6 alkyl group consisting of ethylene oxide and glycidyl groups is substituted with one substituent (preferably one); such that no more than two of R11, R12 and R13 are H (preferably no more than one of R11, R12 and R13 is H);

[0045] Y can be NR 8 Or O (preferably O); and

[0046] R 5 R is an alkyl group, an alkoxy group, an aryloxy group, or a heterocyclic oxygen group with 1 to 20 carbon atoms. 6 and R 7 Independently H or an alkyl group with 1 to 20 carbon atoms, or R 6 and R 7 They can connect together to form alkylene groups with 2 to 5 carbon atoms, thereby forming 3 to 6-membered rings, and R8 It can be H, straight-chain or branched C1-C20 alkyl and aryl.

[0047] When an alkyl, cycloalkyl, or alkyl-substituted aryl group is selected for one of R11, R12, and R13, the alkyl group may be further substituted with a halogen. Therefore, the initiator can be used as the starting molecule for branched or star-shaped (co)polymers. A preferred example is a phenyl group in which one of R11, R12, and R13 is substituted with one to five CCl alkyl substituents, each of which may be independently further substituted with a halogen.

[0048] The transition metal compound in step a) of this disclosure can be any transition metal compound that can participate in redox cycles together with the initiator and the dormant polymer chain but does not form direct carbon-metal bonds with the polymer chain. Preferred transition metal compounds are those of formula M. t Q+ X' Q Of those, M t Q+ The following groups can be freely selected: Cu 1+ Cu 2+ Fe 2+ Fe 3+ Ru 2+ Ru 3+ 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+ Furthermore, X′ is selected from the following groups: halogens, C1-C20-alkoxy groups, and (SO4). 1 / 2 (PO4) 1 / 3 (HPO4) 1 / 2, (H2PO4), trifluoromethanesulfonate, SCN (thiocyanate), hexafluorophosphate, alkylsulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 14 CN and R 15 CO2, where R 14 As defined above, and R 15 It is H or a straight-chain or branched C1-C20 alkyl group (preferably methyl), benzoic acid derivative, aryl or heteroaryl group that can be substituted 1 to 5 times with halogen (preferably substituted 1 to 3 times with fluorine or chlorine); and Q is the formal charge on the metal (e.g., 0 ≤ Q ≤ 7).

[0049] Although any transition metal compound is applicable to this disclosure, transition metal halides, such as copper iodide, copper bromide, or copper chloride, are preferred.

[0050] Suitable ligands for use in this disclosure include ligands having one or more nitrogen, oxygen, phosphorus, and / or sulfur atoms that can coordinate with transition metals via π bonds, and ligands comprising two or more carbon atoms that can coordinate with transition metals via π bonds. Preferred N, O, P, and S-containing ligands may have one of the following formulas:

[0051] R 16 -Z′-R 17

[0052] R 16 -Z′-(R 18 -Z′) L -R 17

[0053] in:

[0054] R 16 and R 17 Independently selected from the group consisting of: H, C1-C20 alkyl, aryl, heterocyclic and C1-C6 alkyl, C1-C4 dialkylamino, C(=Y)R substituted with C1-C6 alkoxy groups. 5 、C=Y)R 6 R 7 and YC(=Y)R 8 Among them, Y and R 5 R 6 R 7 and R 8 As defined above, two or

[0055] R 16 and R 17 They can be linked to form saturated, unsaturated, or heterocyclic rings;

[0056] Z′ represents O, S, and NR. 19 or pR 19 , where R19 Selected from R 16 and R 17 Identical group two

[0057] Each R 18 Independently a divalent group, selected from the group consisting of C2-C4 alkylene (alkanediyl) and C2-C4 alkenyl groups, wherein the covalent bond with each Z′ is in the ortho position (e.g., in a 1,2-arrangement) or the β position (e.g., in a 1,3-arrangement), and selected from C3-C8 cycloalkyldiyl, C3-C8 cycloalkenyldiyl, aryldiyl, and heterocyclic groups, wherein the covalent bond with each Z′ is in the ortho position; and

[0058] L ranges from 1 to 6.

[0059] In addition to the ligands mentioned above, R 16 -Z′ and R 17 Each R in -Z′ that can be combined with Z′ 18 The groups form rings to form linked or fused heterocyclic systems. Alternatively, when R... 16 and / or R 17 When it is a heterocyclic group, in addition to the definition given for Z′ above, Z′ can be a covalent bond (which can be a single or double bond), CH2, or with R. 16 and / or R 17 Fused 4- to 7-membered rings. Exemplary ring systems of the ligands of the present invention include bipyridine, bipyrrole, 1,10-phenanthroline, cryptoids, crown ethers, etc., wherein Z′ is PR 19 R 19 It can also be C1-C20-alkoxy.

[0060] Suitable ligands include pyridine derivatives containing substituents at the 2-position or at both the 2-position and the 6-position, such as those containing a carbonyl moiety, an imine moiety, or a thione moiety.

[0061] Suitable ligands also included in this disclosure are CO (carbon monoxide), porphyrin, and porphycene, wherein the latter two may be substituted with 1 to 6 (preferably 1 to 4) halogen atoms, C1-C6 alkyl groups, C1-C6-alkoxy groups, C1-C6 alkoxycarbonyl groups, aryl groups, heterocyclic groups, and further C1-C6 alkyl groups substituted with 1 to 3 halogens.

[0062] Other ligands suitable for this invention include those of formula R 20 R 21 C(C(=Y)R 5 Compound 2, wherein Y and R 5 As defined above, and R 20 and R 21Each of these is independently selected from the group consisting of: H, halogens, C1-C20 alkyl groups, aryl groups, and heterocyclic groups, and R 20 and R 21 It can be linked to form C3-C8 cycloalkyl rings or hydrogenated (i.e., reduced, non-aromatic, or partially or fully saturated) aromatic or heterocyclic rings, any of which (except H and halogen) can be further substituted by 1 to 5, preferably 1 to 3, C1-C6 alkyl groups, C1-C6 alkoxy groups, halogen atoms, and / or aryl groups. Preferably, R 20 and R 21 One of them is H or a negative charge.

[0063] Other suitable ligands include, for example, ethylenediamine and propylenediamine, which can be substituted one to four times at the amino nitrogen atom by a C1-C4 alkyl group or a carboxymethyl group; aminoethanol and aminopropanol, which can be substituted one to three times at the oxygen and / or nitrogen atom by a C1-C4 alkyl group; ethylene glycol and propylene glycol, which can be substituted once or twice at the oxygen atom by a C1-C4 alkyl group; diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc.

[0064] Suitable carbodied ligands include aromatics and cyclopentadienyl ligands. Preferred carbodied ligands include benzene (which may be substituted with one to six C1-C4 alkyl groups, such as methyl) and cyclopentadienyl (which may be substituted with one to five methyl groups, or may be linked to a second cyclopentadienyl ligand via an ethylene or propylene chain). When using cyclopentadienyl ligands, it is not necessary to include a counter anion (X′) in the transition metal compound.

[0065] Preferred ligands include unsubstituted and substituted pyridines and bipyridines, acetonitrile, (R 10 O)3P、pR 10 3. 1,10-Phenanthroline, porphyrin, cryptoid ligands such as K 222 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 (but not limited to) such ligands are 2,2′-bipyridine, p-alkyl-substituted derivatives of 2,2′-bipyridine, or p-alkoxy-substituted derivatives of 2,2′-bipyridine.

[0066] The molar ratio of initiator, transition metal compound and ligand can be from 1 / 0.01 / 0.02 to 1 / 4 / 12.

[0067] In some embodiments, the macromolecular initiator formed in step a) has formula (V):

[0068] Polyacrylate (X) y (V),

[0069] in:

[0070] "polyacrylate" means polyacrylate produced by ATRP of acrylate monomer (III); X is as defined herein (preferably Cl, Br or I); and y is 1 to 100.

[0071] In some embodiments, step a) of the method of the present invention can be performed simply. In other embodiments, the ATRP material in step a) of the method of the present invention further comprises a solvent.

[0072] In some embodiments, step a) of the method of the present invention is performed at a temperature suitable for ATRP. For example, but not limited to, step a) of the method of the present invention can be performed at a temperature of 40°C to 150°C.

[0073] The amount and proportion of ATRP material in step a) can be adjusted, and are known to those skilled in the art.

[0074] Reaction with α-substituted acrylates

[0075] Step b) of the method of the present invention involves reacting the functionalized polyacrylate prepared in step a) with an α-substituted acrylate, such as an α-(alkyl)acrylate or an α-(polymer-based)acrylate, to form an olefin-acrylate block copolymer. Specifically, step b) of the method of the present invention involves combining reaction materials comprising an α-substituted acrylate and a macromolecular initiator of formula (V) to form an olefin-acrylate block copolymer.

[0076] In some embodiments, the α-substituted acrylate has formula (II):

[0077]

[0078] Where R is a C1-C26 hydrocarbon group or a polyolefin group; and

[0079] R1 is a hydrogen or C1-C30 hydrocarbon group.

[0080] R1 can be any of the implementations described above.

[0081] In some embodiments, R is a C1-C26 hydrocarbon group. In embodiments where R is a C1-C26 hydrocarbon group, R can be a straight-chain, branched, or cyclic C1-C26 alkyl group. For example, R can be a straight-chain, branched, or cyclic alkyl group comprising 1 to 26 carbon atoms, 1 to 10 carbon atoms, or 1 to 8 carbon atoms.

[0082] In another embodiment, R is a polyolefin group. In some embodiments, R is a polyolefin group that may be defined by the properties of RH, wherein the number-average molecular weight of RH is greater than 365 g / mol. In another embodiment, R is a polyolefin group that may be defined by the properties of RH, wherein the number-average molecular weight of RH is greater than 365 g / mol to 10,000,000 g / mol, or greater than 365 g / mol to 5,000,000 g / mol, or greater than 365 g / mol to 1,000,000 g / mol, or greater than 365 g / mol to 750,000 g / mol, or greater than 365 g / mol to 500,000 g / mol, or greater than 365 g / mol to 250,000 g / mol.

[0083] In another embodiment, R is a polyolefin group, which may be defined by the properties of RH, wherein the density of RH is 0.850 g / cc to 0.965 g / cc or 0.860 g / cc to 0.950 g / cc or 0.865 g / cc to 0.925 g / cc.

[0084] In another embodiment, R is a polyolefin group, which may be defined by the properties of RH, wherein the melt index (I2) of RH is 0.01 g / 10 min to 2,000 g / 10 min or 0.01 g / 10 min to 1,500 g / 10 min or 0.1 g / 10 min to 1,000 g / 10 min or 0.1 g / 10 min to 500 g / 10 min or 0.1 g / 10 min to 100 g / 10 min.

[0085] In another embodiment, R is a polyolefin group, which can be defined by the properties of RH, wherein the number-average molecular weight distribution (Mw / Mn or PDI) of RH is 1 to 10, 1 to 7, 1 to 5, or 2 to 4.

[0086] In some embodiments, R is an ethylene homopolymer group comprising units derived from ethylene.

[0087] In some embodiments, R is an ethylene / α-olefin interpolymer group comprising a unit derived from ethylene and at least one C3-C30 α-olefin. The C3-C30 α-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.

[0088] In some embodiments, R is an ethylene / α-olefin copolymer group comprising units derived from ethylene and C3-C30 α-olefins. The C3-C30 α-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.

[0089] In some embodiments, R is an ethylene / α-olefin multiblock interpolymer group or an olefin block copolymer group as defined herein.

[0090] In another embodiment, R is a polymer-based group of a block composite material, a specific block composite material, or a crystalline block composite material as defined herein.

[0091] In some embodiments, R is a propylene homopolymer group comprising units derived from propylene.

[0092] In some embodiments, R is a propylene / α-olefin interpolymer group comprising a unit derived from propylene and at least one comonomer of ethylene or a C3-C30 α-olefin. The C3-C30 α-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.

[0093] In some embodiments, R is a propylene / α-olefin copolymer group comprising a unit derived from propylene and a comonomer of ethylene or a C3-C30 α-olefin. The C3-C30 α-olefin can 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.

[0094] The α-substituted acrylates of formula (II) can be prepared by any suitable method. Non-limiting methods for preparing the α-substituted acrylates of formula (II) are those disclosed in co-pending U.S. Provisional Applications Nos. 62 / 954,941 and 62 / 954,956. For example, the α-substituted acrylates of formula (II) can be prepared by combining materials comprising an α-(halomethyl)acrylate and an organometallic compound of formula R2Zn or R3Al, wherein R is as defined herein. In such non-limiting methods, a nucleophilic substitution reaction occurs, whereby the halogen is a leaving group substituted by the R of the organometallic compound of formula R2Zn or R3Al.

[0095] In some embodiments, the olefin-acrylate block copolymer obtained by the method of the present invention has formula (VI):

[0096]

[0097] Each of “polyacrylate”, R, R1, X and y is as defined herein, and m is 1 to 50.

[0098] As shown in Formula (VI), the polymer structure of the olefin-acrylate block copolymer prepared by the method of this disclosure can be varied. Examples of polymer structures include linear diblock copolymers, hyperbranched diblock copolymers, multi-arm diblock copolymers, and comb / brush diblock copolymers. For example, in step b), when using a monofunctional ATRP initiator (y = 1), adding an equivalent of α-substituted acrylate to the macromolecular initiator will prepare a linear diblock copolymer, and adding an "m" equivalent of α-substituted acrylate to the macromolecular initiator will prepare a diblock copolymer having comb-shaped polyolefin blocks.

[0099] In some embodiments, step b) of the method of the present invention can be performed simply. In other embodiments, the reaction materials in step b) of the method of the present invention further include a solvent.

[0100] For example, but not limited to, step b) of the method of the present invention can be performed at a temperature of 40°C to 150°C.

[0101] The amount and ratio of the reactants in step b) can be adjusted and are known to those skilled in the art.

[0102] The method of the present invention can be described in, but is not limited to, the following schemes.

[0103]

[0104] The specific implementation schemes disclosed herein include, but are not limited to, the following:

[0105] 1. A method for preparing olefin-acrylate block copolymers, the method comprising:

[0106] a) ATRP is performed by combining materials containing acrylate monomers, initiators with radical-transferable atoms or groups, transition metal compounds, and ligands to form macromolecular initiators; and

[0107] b) Combining reactive materials comprising α-substituted acrylates and the macromolecular initiator to form the olefin-acrylate block copolymer.

[0108] 2. The method according to implementation scheme 1, wherein:

[0109] The α-substituted acrylate has formula (II):

[0110]

[0111] The acrylate monomer has formula (III):

[0112]

[0113] The initiator has formula (IV):

[0114]

[0115] The macromolecular initiator has the formula (V):

[0116] Polyacrylate-(X) y (V);

[0117] The olefin-acrylate block copolymer has formula (VI):

[0118] in:

[0119] Each R1 is independently a hydrogen or C1-C30 hydrocarbon group;

[0120] Each R2 is independently a hydrogen or methyl group;

[0121] Each R is independently a C1-C26 hydrocarbon group or a polyolefin group;

[0122] m ranges from 1 to 50;

[0123] Each y is independently between 1 and 100;

[0124] Each X is independently selected from the group consisting of: halide ions (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 )2, where R 14 It is an aryl or straight-chain or branched C1-C20 (preferably C1-C10) alkyl group, or when N(R 14 When the )2 group is present, the two R groups 14 The groups can connect to form 5, 6, or 7-membered heterocycles, and R... 10 It is an alkyl group with 1 to 20 carbon atoms, wherein each hydrogen atom can be independently replaced by a halide ion;

[0125] R11, R12, and R13 are each independently selected from the group consisting of: H, halide ions, C1-C20 alkyl (preferably C1-C10 alkyl, and 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, and more preferably vinyl), ethylene oxide, glycidyl, aryl, heterocyclic, aralkyl, arylalkylene (aryl-substituted alkenyl, and the alkenyl is a vinyl that can be substituted by one or two C1-C6 alkyl groups and / or halogen atoms, preferably chlorine-substituted), C1-C6 alkyl groups wherein one to all hydrogen atoms (preferably one) are substituted by a halogen (preferably fluorine or chlorine, wherein one or more hydrogen atoms are substituted, and preferably fluorine, chlorine or bromine, wherein one hydrogen atom is substituted) and C1-C6 alkyl groups substituted by one to three C1-C4 alkoxy, aryl, heterocyclic, C(=Y)R 6 C(=Y)NR 6 R 7 The C1-C6 alkyl group consisting of ethylene oxide and glycidyl groups is substituted with one substituent (preferably one); such that no more than two of R11, R12 and R13 are H (preferably no more than one of R11, R12 and R13 is H);

[0126] Y can be NR 8 Or O (preferably O);

[0127] R 5 R is an alkyl group, an alkoxy group, an aryloxy group, or a heterocyclic oxygen group with 1 to 20 carbon atoms. 6 and R 7 Independently H or an alkyl group with 1 to 20 carbon atoms, or R 6 and R 7 They can connect together to form alkylene groups with 2 to 5 carbon atoms, thereby forming 3 to 6-membered rings, and R 8 It is H, straight-chain or branched C1-C20 alkyl and aryl diand

[0128] "Polyacrylate" refers to the polyacrylate produced by ATRP of the acrylate monomer.

[0129] 3. The method according to any one of the foregoing embodiments, wherein each R1 is independently a straight-chain, branched, or cyclic C1-C30, C1-C10, or C1-C8 alkyl group.

[0130] 4. The method according to any one of the foregoing embodiments, wherein each R is independently a C1-C26 hydrocarbon group.

[0131] 5. The method according to embodiment 4, wherein each R is independently a straight-chain, branched, or cyclic C1-C26, C1-C10, or C1-C8 alkyl group.

[0132] 6. The method according to any one of embodiments 1 to 3, wherein each R is independently a polyolefin group.

[0133] 7. The method according to embodiment 6, wherein the polyolefin group is a vinyl polymer group.

[0134] 8. The method according to embodiment 7, wherein the polyolefin group is an ethylene homopolymer group comprising units derived from ethylene.

[0135] 9. The method according to embodiment 7, wherein the polyolefin group is an ethylene / α-olefin interpolymer group comprising units derived from ethylene and C3-C30 α-olefins.

[0136] 10. The method according to embodiment 7, wherein the polyolefin group is an ethylene / α-olefin copolymer group comprising units derived from ethylene and C3-C30 α-olefins.

[0137] 11. The method according to embodiment 9 or 10, wherein the C3-C30 α-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.

[0138] 12. The method according to embodiment 7, wherein the polyolefin group is an ethylene / α-olefin multiblock interpolymer group.

[0139] 13. The method according to embodiment 6, wherein the polyolefin group is selected from the group consisting of: block complexes, designated block complexes, and polymeric groups of crystalline block complexes.

[0140] 14. The method according to embodiment 6, wherein the polyolefin group is a propylene polymer group.

[0141] 15. The method according to embodiment 14, wherein the polyolefin group is a propylene homopolymer group comprising units derived from propylene.

[0142] 16. The method according to embodiment 14, wherein the polyolefin group is a propylene / α-olefin interpolymer group comprising units derived from propylene and ethylene or C4-C30 α-olefins.

[0143] 17. The method according to embodiment 14, wherein the polyolefin group is a propylene / α-olefin copolymer group comprising units derived from propylene and ethylene or C4-C30 α-olefins.

[0144] 18. The method according to embodiment 16 or 17, wherein the C4-C30 α-olefin is selected from the group consisting of 1-butene, 1-hexene and 1-octene.

[0145] 19. The method according to any one of embodiments 6 to 18, wherein the polyolefin group can be defined by the properties of RH, and wherein the number-average molecular weight of RH is greater than 365 g / mol.

[0146] 20. The method according to any one of embodiments 6 to 19, wherein the polyolefin group may be defined by the properties of RH, and wherein the number average molecular weight of RH is greater than 365 g / mol to 10,000,000 g / mol or greater than 365 g / mol to 5,000,000 g / mol or greater than 365 g / mol to 1,000,000 g / mol or greater than 365 g / mol to 750,000 g / mol or greater than 365 g / mol to 500,000 g / mol or greater than 365 g / mol to 250,000 g / mol.

[0147] 21. The method according to any one of embodiments 6 to 20, wherein the polyolefin group may be defined by the properties of RH, and wherein the density of RH is 0.850 g / cc to 0.965 g / cc or 0.860 g / cc to 0.950 g / cc or 0.865 g / cc to 0.925 g / cc.

[0148] 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 wherein the melt index (I2) of RH is 0.01 g / 10 min to 2,000 g / 10 min or 0.01 g / 10 min to 1,500 g / 10 min or 0.1 g / 10 min to 1,000 g / 10 min or 0.1 g / 10 min to 500 g / 10 min or 0.1 g / 10 min to 100 g / 10 min.

[0149] 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 wherein the number-average molecular weight distribution (Mw / Mn) of RH is 1 to 10 or 1 to 7 or 1 to 5 or 2 to 4.

[0150] 24. The method according to any one of embodiments 2-23, wherein y is 1 and m is 1.

[0151] 25. The method according to any one of the foregoing embodiments, wherein each of steps a) and b) is performed at a temperature of 40°C to 150°C.

[0152] 26. The method according to any one of the foregoing embodiments, wherein the α-substituted acrylate is prepared by a method comprising combining a starting material comprising an α-(halomethyl)acrylate and an organometallic compound of formula R2Zn or R3Al, wherein the α-(halomethyl)acrylate has formula (I):

[0153] in:

[0154] X is a halide ion, and R and R1 are as defined above.

[0155] 27. The method according to any one of the foregoing embodiments, wherein the transition metal compound is a transition metal halide, and wherein the ligand is an N, O, P or S ligand coordinated with the transition metal compound by a σ bond or a π bond, or any C-containing compound that can be coordinated with the transition metal compound by a π bond.

[0156] 28. The method according to any one of the foregoing embodiments, wherein the ATRP material and / or the reaction material further comprises a solvent.

[0157] 29. An olefin-acrylate block copolymer having formula (VI):

[0158] Two of them

[0159] "Polyacrylate" refers to the polyacrylate diacrylate produced by atom transfer radical polymerization (ATRP) of acrylate monomers.

[0160] R1 is a hydrogen or C1-C30 hydrocarbon group.

[0161] R is a C1-C26 hydrocarbon group or a polyolefin group;

[0162] m is 1 to 50.

[0163] y is 1 to 100 and

[0164] X is selected from the group consisting of: halide ions (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) OR14 ON(R) 14 )2 and SC(=S)N(R 14 )2, where R 14 It is an aryl or straight-chain or branched C1-C20 (preferably C1-C10) alkyl group, or when N(R 14 When the )2 group is present, the two R groups 14 The groups can connect to form 5, 6, or 7-membered heterocycles, and R... 10 It is an alkyl group with 1 to 20 carbon atoms, wherein each hydrogen atom can be independently replaced by a halide ion.

[0165] 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.

[0166] 31. The olefin-acrylate block copolymer according to embodiment 29 or 30, wherein R is a C1-C26 hydrocarbon group.

[0167] 32. The olefin-acrylate block copolymer according to embodiment 31, wherein R is a linear, branched or cyclic C1-C26 or C1-C10 or C1-C8 alkyl group.

[0168] 33. The olefin-acrylate block copolymer according to embodiment 29 or 30, wherein R is a polyolefin group.

[0169] 34. The olefin-acrylate block copolymer according to embodiment 33, wherein the polyolefin group is a vinyl polymer group.

[0170] 35. The olefin-acrylate block copolymer according to embodiment 34, wherein the polyolefin group is an ethylene homopolymer group comprising units derived from ethylene.

[0171] 36. The olefin-acrylate block copolymer according to embodiment 34, wherein the polyolefin group is an ethylene / α-olefin interpolymer group comprising units derived from ethylene and C3-C30 α-olefins.

[0172] 37. The olefin-acrylate block copolymer according to embodiment 34, wherein the polyolefin group is an ethylene / α-olefin copolymer group comprising units derived from ethylene and C3-C30 α-olefins.

[0173] 38. The olefin-acrylate block copolymer according to embodiment 36 or 37, wherein the C3-C30 α-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.

[0174] 39. The olefin-acrylate block copolymer according to embodiment 34, wherein the polyolefin group is an ethylene / α-olefin multiblock interpolymer group.

[0175] 40. The olefin-acrylate block copolymer according to embodiment 33, wherein the polyolefin group is selected from the group consisting of: block complexes, designated block complexes and polymeric groups of crystalline block complexes.

[0176] 41. The olefin-acrylate block copolymer according to embodiment 33, wherein the polyolefin group is a propylene polymer group.

[0177] 42. The olefin-acrylate block copolymer according to embodiment 41, wherein the polyolefin group is a propylene homopolymer group comprising units derived from propylene.

[0178] 43. The olefin-acrylate block copolymer according to embodiment 41, wherein the polyolefin group is a propylene / α-olefin interpolymer group comprising units derived from propylene and ethylene or C4-C30 α-olefins.

[0179] 44. The olefin-acrylate block copolymer according to embodiment 41, wherein the polyolefin group is a propylene / α-olefin copolymer group comprising units derived from propylene and ethylene or C4-C30 α-olefins.

[0180] 45. The olefin-acrylate block copolymer according to embodiment 43 or 44, wherein the C4-C30 α-olefin is selected from the group consisting of 1-butene, 1-hexene and 1-octene.

[0181] 46. ​​An 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 wherein the number average molecular weight of RH is greater than 365 g / mol.

[0182] 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 wherein the number average molecular weight of RH is greater than 365 g / mol to 10,000,000 g / mol or greater than 365 g / mol to 5,000,000 g / mol or greater than 365 g / mol to 1,000,000 g / mol or greater than 365 g / mol to 750,000 g / mol or greater than 365 g / mol to 500,000 g / mol or greater than 365 g / mol to 250,000 g / mol.

[0183] 48. 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 wherein the density of RH is 0.850 g / cc to 0.965 g / cc or 0.860 g / cc to 0.950 g / cc or 0.865 g / cc to 0.925 g / cc.

[0184] The polyolefin group can be defined by the properties of RH, and the melt index (I2) of RH is 0.01 g / 10 min to 2,000 g / 10 min or 0.01 g / 10 min to 1,500 g / 10 min or 0.1 g / 10 min to 1,000 g / 10 min or 0.1 g / 10 min to 500 g / 10 min or 0.1 g / 10 min to 100 g / 10 min.

[0185] 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 wherein the number-average molecular weight distribution (Mw / Mn) of RH is 1 to 10, 1 to 7, 1 to 5, or 2 to 4.

[0186] 50. An olefin-acrylate block copolymer according to any one of embodiments 33-49, wherein y is 1 and m is 1.

[0187] 51. An olefin-acrylate block copolymer according to any one of embodiments 33-50, wherein the acrylate monomer has formula (III):

[0188] R1 is a hydrogen or C1-C30 hydrocarbon group and R2 is a hydrogen or methyl group.

[0189] Test methods

[0190] density :

[0191] Density is measured according to ASTM D-792, Method B.

[0192] Melt index :

[0193] Melt index (I2) was measured according to ASTM D-1238 (incorporated herein by reference in its entirety), conditions 190°C / 2.16 kg, and reported in grams eluted every 10 minutes.

[0194] GPC

[0195] The following properties of the polymer samples were tested using GPC.

[0196] Molecular weight (MW) and molecular weight distribution (MWD) were determined using a high-temperature gel permeation chromatography (GPC IR) system consisting of an infrared concentration detector (IR-5) from PolymerChar Inc. (Valencia, Spain). The carrier solvent was 1,2,4-trichlorobenzene (TCB). The autosampler chamber was operated at 160 °C, and the column chamber at 150 °C. The columns used were four Polymer Laboratories Mixed ALS, 20 μm columns. The chromatographic solvent (TCB) and sample preparation solvent were from the same solvent source, containing 250 ppm butylated hydroxytoluene (BHT) and nitrogen injection. The sample was prepared in TCB at a concentration of 2 mg / mL. The polymer sample was gently shaken at 160 °C for 2 h. The injection volume was 200 μL, and the flow rate was 1.0 mL / min.

[0197] The GPC column assembly was calibrated using 21 polystyrene standards with narrow molecular weight distributions. The standards ranged in molecular weight from 580 to 8,400,000 g / mol and were arranged in a mixture of six "cocktails" with at least a decimal interval between individual molecular weights.

[0198] The GPC column assembly was calibrated before running the examples using twenty-one narrow molecular weight distribution polystyrene standards. The standards had molecular weights (Mw) ranging from 580 to 8,400,000 g / mol and were contained in six “cocktail” mixtures. Each standard mixture was separated by at least a decimal place from the individual molecular weights. The standard mixtures were purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards were prepared as follows: for molecular weights equal to or greater than 1,000,000 g / mol, 0.025 g in 50 mL of solvent; and for molecular weights less than 1,000,000 g / mol, 0.025 g in 50 mL of solvent. Gently stir for 30 minutes to dissolve the polystyrene standards at 80°C. First, run the narrow standard mixture, proceeding in order of decreasing molecular weight (Mw) of the components to minimize degradation. Use the Mark-Houwink constant to convert the peak molecular weight of the polystyrene standards to polyethylene Mw. After obtaining the constant, use these two values ​​to construct two linear reference conventional calibration values ​​for polyethylene molecular weight and intrinsic viscosity as a function of the elution column.

[0199] The peak molecular weight of polystyrene standards was converted to the molecular weight of polyethylene using the following equation (as described by Williams and Ward, *Journal of Polymer Science: Polymer Letters*, 6, 621 (1968)):

[0200] M (polyethylene) = A (M (polystyrene)) B (1)

[0201] Here, the value of B is 1.0, while the experimentally measured value of A is approximately 0.41.

[0202] The corresponding polyethylene-equivalent calibration point obtained from equation (1) is fitted to the elution volume of the observed polystyrene standard using a third-order polynomial.

[0203] Calculate the number-average molecular weight, weight-average molecular weight, and z-average molecular weight using the following equations:

[0204]

[0205]

[0206] Among them, Wf i It is the weight fraction of the i-th component, and M i It is the molecular weight of the i-th component.

[0207] MWD is expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn).

[0208] The accurate value of A is determined by adjusting the value of A in equation (1) until the Mw calculated using equation (3) and the corresponding retention volume polynomial is consistent with the known value of Mw of 120,000 g / mol for the standard linear polyethylene homopolymer reference.

[0209] The GPC system consists of a Waters (Milford, Massachusetts) 150°C high-temperature chromatograph equipped with an organic differential refractometer (RI) (other suitable high-temperature GPC instruments include PolymerLab (Shropshire, UK) Model 210 and Model 220). Additional detectors may include an IR4 infrared detector from PolymerChAR (Valencia, Spain), a precision detector from Amherst, Massachusetts, a dual-angle laser scattering detector Model 2040, and a Viscotek (Houston, Texas) 150R 4 capillary solution viscometer. A GPC with the last two independent detectors and at least one of the first detectors is sometimes referred to as a "3D-GPC," while the term "GPC" alone usually refers to a conventional GPC. Depending on the sample, a 15-degree or 90-degree angle of the light scattering detector is used for computational purposes.

[0210] Data collection was performed using Viscotek TriSEC software version 3 and a 4-channel Viscotek Data Manager DM400. The system was equipped with an online solvent degassing unit from Polymer Laboratories (Shropshire, UK). Suitable high-temperature GPC columns could be used, such as four 30 cm long Shodex HT803 13 μm columns or four 30 cm Polymer Labs columns (MixA LS, Polymer Laboratories) with 20 μm mixed pore size packing. The sample turntable chamber was operated at 140 °C, and the column chamber at 150 °C. The sample was prepared at a concentration of 0.1 g of polymer in 50 mL of solvent. Both the chromatographic solvent and the sample preparation solvent contained 200 ppm butylated hydroxytoluene (BHT). Both solvents were sprayed with nitrogen. The polyethylene sample was gently stirred at 160 °C for four hours (4 h). The injection volume was 200 μL. The flow rate through the GPC was set to 1 mL / min.

[0211] NMR(( 13 C and 1 H) :

[0212] NMR analysis was performed at room temperature using standard NMR solvents such as chloroform or benzene, and data were acquired on a Varian 500MHz spectrometer.

[0213] Diffusion NMR: The experiment employed 2048 scans with a repetition time of 15 seconds. Spectra were centered at 90 ppm and covered a bandwidth of 240 ppm. The self-diffusion coefficient (D) was measured using pulsed field gradient NMR via diffusion detected at 1H and 13C, where the echoes from the dual-stimulation method mitigate any artifacts through thermal convection. Typically, this method utilizes the spatial variation of a magnetic field (i.e., the magnetic field gradient (g)) to physically label the spatial location of molecular integration over well-defined time intervals, thereby coupling the NMR peak intensity to the self-diffusion (D) of each molecule. D was quantized using the Stejskal-Tanner equation (Equation 5), where I and I0 represent the NMR signal intensity with / without gradient. γ is the gyromagnetic ratio of the nuclei, g is the gradient intensity, δ is the gradient pulse duration, and Δ is the diffusion time. Given that peaks from the same molecule must produce the same D, this type of method enables the intrinsic separation of NMR peaks by the D associated with each peak without compromising spectral resolution. This method can essentially be considered an analogue of size exclusion chromatography (SEC), where large molecules diffuse slowly / elute earlier, or vice versa. Therefore, the measurement provides explicit intermolecular information by comparing D... 端 With D 主链 This indicates whether the polymer backbone is capped by specific end groups.

[0214]

[0215] GCMS. :

[0216] The following tandem gas chromatography / low-resolution mass spectrometry was performed at 70 eV using electron shock ionization (EI) 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 μm):

[0217] Programmatic approach:

[0218] Oven equilibration time at 50℃ for 0.5 minutes.

[0219] Then increase the temperature from 25°C / min to 200°C and hold for 5 min.

[0220] Running time 11 minutes

[0221] Example

[0222] The following examples 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.

[0223] Unless otherwise stated, all materials and reagents are commercially available, for example from Sigma Aldrich.

[0224] Example 1

[0225]

[0226] The reaction in Example 1 was carried out in a glove box under an inert nitrogen atmosphere and according to the exemplary and non-limiting reaction protocol described above. 5.88 mL of 0.30 M dioctyl zinc was added to Isopar TM The solution from 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 heated dioctyl zinc solution. During the slow addition, the solution changed from light brown to clear and then became cloudy with a visible white precipitate. After several minutes, the precipitate settled into a sticky yellow residue at the bottom of the vial. After 48 hours at 60 °C, 83 mg of hexamethylenebenzene (0.511 mmol) was added as an NMR internal standard. The NMR conversion was calculated to be 62.6%. NMR analysis is shown in [Figure / Reference]. Figure 1A and Figure 1B In the middle. For example Figure 1C and Figure 1D As observed, GC-MS of the reaction aliquots showed the formation of the desired product (the lower retention time peak corresponds to Isopar). TM E). The reaction was quenched with water. Purification was performed by column chromatography using a mixture of 2% ethyl acetate / hexane to remove Zn salt and internal standard. 405 mg of product (51%) was separated.

[0227] Example 2

[0228]

[0229] The reaction was carried out in a nitrogen-atmospheric 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 column to remove inhibitors. 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. Deoxyacetone (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 until a Cu complex formed, approximately 20 minutes. After the complex formed, 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 was observed, indicating that polymerization had occurred. After confirming by NMR that most of the monomers had reacted, methyl 2-methylene undecanoate (0.232 g, 1.09 mmol) was added and the reaction was stirred overnight at 55 °C.

[0230] By NMR (see Figure 2A and Figure 2B All compounds prepared in Example 1 had reacted after reacting 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 decompose the polymer into cold hexane were unsuccessful. The solvent was removed on a rotary evaporator to give a viscous yellow polymer. The polymer was washed with chlorobenzene to remove excess hexane and THF and dried overnight under vacuum at 70°C.

[0231] According to GPC: Mw = 3726, Mn = 3125, and PDI = 1.19.

[0232] Example 3

[0233]

[0234] The reaction was carried out in a nitrogen-atmospheric glove box according to the ATRP procedure described in Macromolecules Vol. 33, 4039-4047, 2000. t-BA was passed through an alumina column to remove inhibitors before the reaction began. CuBr (78.2 mg, 0.545 mmol) and CuBr2 (6.0 mg, 0.027 mmol) were added to a dry 20 mL vial. Deoxyacetone (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 until a Cu complex formed, approximately 20 minutes. 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. Three hours later, before all monomers reacted, the reaction was terminated by adding THF to the reaction mixture and passing the solution through an alumina stopper to remove the Cu catalyst. THF was removed on a rotary evaporator, followed by drying on a Schlenk line at 70°C over the entire weekend 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(tert-butyl acrylate) was used for the next step.

[0235] 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 stir bar. PMDETA (0.023 mL, 0.110 mmol) was added, and the mixture was stirred for 20 minutes. 2.37 mL of a poly(tert-butyl acrylate) macromolecular initiator solution was injected into the reaction vial via syringe. The initial sample was removed, and the reaction was stirred at 55 °C. After overnight reaction, NMR showed a conversion of approximately 30%. The acetone solvent was partially removed with nitrogen to increase the concentration of the reactants.

[0236] After 36 hours, the reaction was terminated by removing the vial from the heating block, adding approximately 20 mL of THF, and passing the solution through an alumina stopper to remove the copper catalyst. Attempts to decompose the polymer into cold hexane were unsuccessful. The solution was dried on a rotary evaporator, washed with chlorobenzene to remove excess hexane and THF, and dried overnight under vacuum at 70°C.

[0237] The NMR spectrum of Example 3 is shown in [reference]. Figure 3A and Figure 3B .

[0238] GPC: Mw = 6906, Mn = 5795, and PDI = 1.19. ¹H NMR: Mn = 5250.

Claims

1. A method for making an olefin-acrylate block copolymer, the method comprising: a) conducting atom transfer radical polymerization (ATRP) by combining ATRP materials comprising an acrylate monomer, an initiator having a radicalically transferable atom or group, a transition metal compound, and a ligand, thereby forming a macroinitiator; and b) combining reaction materials comprising an alpha-substituted acrylate and the macroinitiator, thereby forming the olefin-acrylate block copolymer, wherein: the alpha-substituted acrylate is of formula (II): the acrylate monomer is of formula (III): the initiator is of formula (IV): the macroinitiator is of formula (V): polyacrylate-(X) y (V); the olefin-acrylate block copolymer is of formula (VI): wherein: each R1is independently hydrogen or a C1-C30 hydrocarbyl group; each R2is independently hydrogen or a methyl group; each R is independently a polyolefinic group; m is 1 to 50; each y is independently 1 to 100; each X is independently selected from the group consisting of: halide, OR 10 , SR 14 , SeR 14 , -SCN (thiocyanato), OC(=0)R 14 , OP(=0)R 14 , OP(=O)(OR 14 )2, OP(=O)OR 14 , O-N(R 14 )2, and S-C(=S)N(R 14 )2, wherein R 14 is an aryl or straight-chain or branched C1-C20 alkyl group, or when the N(R 14 )2 group is present, the two R 14 groups can be joined to form a 5-, 6- or 7-membered heterocyclic ring, and wherein R 10 is an alkyl group of 1 to 20 carbon atoms, wherein each hydrogen atom can be independently replaced by a halide; R11, R12and R13are each independently selected from the group consisting of H, halide, C1-C20alkyl, C3-C8cycloalkyl, C(=Y)R 5 , C(=Y)NR 6 R 7 , COCl, OH, CN, C2-C20alkenyl or alkynyl, oxiranyl, glycidyl, aryl, heterocyclyl, aralkyl, aralkenyl, C1-C6alkyl wherein one to all hydrogen atoms are replaced by halogen and C1-C6alkyl substituted with one to three substituents selected from the group consisting of C1-C4alkoxy, aryl, heterocyclyl, C(=Y)R 6 , C(=Y)NR 6 R 7 , oxiranyl and glycidyl; with the proviso that not more than two of R11, R12and R13are H; Y can be NR 8 or O; R 5 alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, aryloxy or heterocaryloxy, R 6 and R 7 are independently H or alkyl of 1 to 20 carbon atoms, or R 6 and R 7 is an alkylene group capable of being linked together to form 2 to 5 carbon atoms, thereby forming a 3 to 6 membered ring, and R 8 is H, linear or branched C1-C20 alkyl and aryl; and "polyacrylate" means the polyacrylate resulting from the ATRP of the acrylate monomer.

2. The method of claim 1, wherein the polyolefinic group is an ethylene-based polymeric group.

3. The method of claim 1, wherein the polyolefinic group is a propylene-based polymeric group.

4. The method of any one of claims 1 to 3, wherein the polyolefinic group can be defined by the nature of R-H, and wherein the number average molecular weight of R-H is greater than 365 g / mol.

5. The method of any one of claims 1 to 3, wherein the halogen atom is chlorine.

6. The method of any one of claims 1 to 3, wherein each of steps a) and b) is conducted at a temperature of 40 °C to 150 °C.

7. The method of claim 1, wherein the alkenyl group in the aralkenyl group is a vinyl group.

8. The method of claim 1, wherein the alkenyl group in the aralkenyl group is a vinyl group substituted with one or two C1-C6 alkyl groups and / or halogen atoms.

9. An olefin-acrylate block copolymer made by the method of any one of claims 1-8.

10. An olefin-acrylate block copolymer of formula (VI): wherein: "polyacrylate" means a polyacrylate resulting from atom transfer radical polymerization (ATRP) of an acrylate monomer; R1is hydrogen or a C1-C30 hydrocarbyl group; R is a polyolefinic group; m is 1 to 50; y is 1 to 100; and X is selected from the group consisting of: halide, OR 10 , SR 14 , SeR 14 , -SCN (thiocyanate), OC(=0)R 14 , OP(=0)R 14 , OP(=0)(OR 14 )2, OP(=0)OR 14 , 0-N(R 14 )2, and S-C(=S)N(R 14 )2, wherein R 14 is an aryl or straight chained or branched C1-C20 alkyl group, or when a N(R 14 )2 group is present, the two R 14 groups can be joined to form a 5, 6, or 7 membered heterocyclic ring, and wherein R 10 is an alkyl of 1 to 20 carbon atoms, wherein each hydrogen atom can be independently replaced by a halide.

11. The olefin-acrylate block copolymer of claim 10, wherein the halide is selected from the group consisting of CI, Br, and I.

12. The olefin-acrylate block copolymer of claim 10, wherein the linear or branched C1-C20 alkyl group is a linear or branched C1-C10 alkyl group.

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