Method for preparing olefin-acrylate diblock copolymers

Abstract

The present disclosure relates to a method for preparing an olefin-acrylate diblock copolymer, the method comprising: a) performing nitroxide mediated polymerization (NMP) by combining NMP materials comprising an acrylate monomer and a nitroxide initiator, thereby forming a nitroxide macroinitiator; and b) combining an end-capping reaction material comprising an alpha-substituted acrylate and the nitroxide macroinitiator, thereby forming an olefin-acrylate diblock copolymer.

Description

[Background technology]

[0001] Cross-reference of related applications This application claims priority to U.S. Patent Application No. 62 / 954,941, filed on 30 December 2019, which is incorporated herein by reference in its entirety.

[0002] This disclosure relates to a method for synthesizing olefin-acrylate diblock copolymers using nitroxide-mediated polymerization (NMP) of acrylate monomers, and then preparing functionalized polyacrylates that are end-capped 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 NMP methods well known in the art are employed as end-capping monomers for the polyacrylates produced by NMP in order to produce olefin-acrylate diblock copolymers. This method has not been realized to date up to the disclosure of this application. [Overview of the project]

[0003] This disclosure relates to a method for preparing olefin-acrylate diblock copolymers, the method being described below: a) Performing NMP by combining acrylate monomers and nitroxide initiators in a nitroxide-mediated polymerization (NMP) material, thereby forming a nitroxide polymer initiator, b) Combining end-capping reaction materials containing an alpha-substituted acrylate and a nitroxide polymer initiator, thereby forming an olefin-acrylate diblock copolymer. [Brief explanation of the drawing]

[0004] [Figure 1A]Figures 1A and 1B provide the 1H NMR and 13C NMR spectra of Example 1, respectively. [Figure 1B] Figures 1A and 1B provide the 1H NMR and 13C NMR spectra of Example 1, respectively. [Modes for carrying out the invention]

[0005] definition All references to the periodic table in this specification refer to the periodic table published and copyrighted by CRC Press, Inc. in 2003. 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.

[0006] Unless otherwise stated, suggested by the context, or customary in the art, all parts and percentages are based on weight.

[0007] 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 synthesis techniques, definitions (to the extent that they do not conflict with any definitions provided herein), and general knowledge in the art (or their equivalent U.S. editions are incorporated herein by reference).

[0008] The 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 that include explicit values ​​(e.g., 1 or 2, or 3 to 5, or 6 or 7), any subranges between any two explicit values ​​(e.g., 1 to 2, 2 to 6, 5 to 7, 3 to 7, 5 to 6, etc.) are included. The numerical ranges disclosed herein further include fractions between any two explicit values.

[0009] 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 that are not essential to the operability and excludes any other components, processes, or procedures from the scope of any subsequent description. The term “consisting of” excludes any components, processes, or procedures that are not specifically described or enumerated. The term “or” refers to the enumerated items individually and in any combination, unless otherwise stated.

[0010] 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.

[0011] 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.

[0012] The term "polymer" refers to a material prepared by reacting (i.e., polymerizing) a set of monomers, which may be a homogeneous (i.e., single) set of monomers or a heterogeneous (i.e., two or more) set of monomers. As used herein, the term polymer includes the term "homopolymer," which refers to a polymer prepared from a homogeneous set of monomers, and the term "interpolymer," as defined below.

[0013] 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.

[0014] "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."

[0015] 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 its 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 also contains residual amounts of other components.

[0016] 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.”

[0017] 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.

[0018] As used herein, the terms “ethylene / alpha-olefin multiblock interpolymer” or “olefin block copolymer” refer 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, the 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 linked end to end (covalently) with respect to the polymerized functional groups, rather than in a pendant or grafted manner. The blocks differ in the amount or type of comonomers incorporated therein, density, amount of crystallinity, 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 having unique distributions in both polymer molecular weight distribution (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 olefin block copolymers of this disclosure and methods for preparing them are disclosed in U.S. Patent Nos. 7,858,706(B2), 8,198,374(B2), 8,318,864(B2), 8,609,779(B2), 8,710,143(B2), 8,785,551(B2) and 9,243,090(B2), all of which are incorporated herein by reference.

[0019] 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 number of moles of polymerized monomer units in the ethylene-based polymer (EP); (ii) an alpha-olefin-based polymer (AOP) (hard copolymer) having an alpha-olefin content exceeding 90 mol% based on the total number of moles of polymerized monomer units in the alpha-olefin-based polymer (AOP); and (iii) a block copolymer (diblock copolymer) having an ethylene block (EB) and an alpha-olefin block (AOB), where the ethylene block of the block copolymer has the same composition as the EP of component (i) of the block composite, and the alpha-olefin block of the block copolymer has the same composition as the AOP of component (ii) of the block composite. In addition, the compositional distribution between the amount of EP and the amount of AOP in the block composite will be essentially the same as the compositional distribution between the corresponding blocks in the block copolymer. Non-limiting examples of the block composites of this disclosure, as well as methods 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.

[0020] 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 number of moles of polymerized monomer units in the ethylene-based polymer (EP); (ii) an alpha-olefin-based polymer (AOP) (hard copolymer) having an alpha-olefin content of 61 mol% to 90 mol / 1% based on the total number of moles of polymerized monomer units in the alpha-olefin-based polymer (AOP); and (iii) a block copolymer (diblock copolymer) having an ethylene block (EB) and an alpha-olefin block (AOB), 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 amount of EP and the amount of 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 methods for preparing them, are disclosed in their entirety in WO2017 / 044547, which is incorporated herein by reference.

[0021] The term "crystalline block composite: CBC" refers to a polymer containing three polymer components: (i) a crystalline ethylene-based polymer (CEP) having an ethylene content of more than 90 mol% based on the total number of moles of polymerized monomer units in the crystalline ethylene-based polymer (CEP); (ii) a crystalline alpha-olefin-based polymer (CAOP), which is a crystalline alpha-olefin-based copolymer (CAOP) having an alpha-olefin content of more than 90 mol% based on the total number of moles of polymerized monomer units in the crystalline alpha-olefin-based copolymer (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 composite, and the CAOB of the block copolymer has the same composition as the CAOP of component (ii) of the crystalline block composite. In addition, the composition distribution between the amount of CEP and the amount of CAOP in the crystalline block composite will be essentially the same as the composition distribution between the corresponding blocks in the block copolymer. Non-limiting examples of the crystalline block composites of the present disclosure, as well as methods for preparing them, are disclosed in U.S. Patent No. 8,822,598 (B2) and International Publication No. 2016 / 01028961 (A1), which are hereby incorporated by reference in their entirety.

[0022] "Propylene-based polymer" is a polymer that contains a majority amount of polymerized propylene, and optionally may further contain polymerized units of at least one comonomer, based on the weight of the polymer. "Propylene-based interpolymer" is an interpolymer that contains a majority amount of polymerized propylene in its polymerized form and further contains polymerized units of at least one comonomer, based on the weight of the interpolymer. "Propylene homopolymer" is a polymer that contains repeating units derived from propylene but contains residual amounts of other components.

[0023] As used herein, the term "propylene / alpha-olefin interpolymer" refers to a polymer that contains, in polymerized form, a majority 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. The propylene / alpha-olefin interpolymer can be a random or block interpolymer. The term "propylene / alpha-olefin interpolymer" includes the term "propylene / alpha-olefin copolymer".

[0024] As used herein, the term "propylene / alpha-olefin copolymer" refers to a copolymer that contains, in polymerized form, a majority weight percent of propylene (based on the weight of the copolymer) and a comonomer that is an alpha-olefin, where propylene and the alpha-olefin are the only two monomer types. The propylene / alpha-olefin copolymer can be a random or block copolymer.

[0025] Terms such as "polymeryl", "polymeryl group", etc. refer to a polymer lacking one hydrogen.

[0026] Terms such as "polyolefinyl", "polyolefinyl group", etc. refer to a polyolefin lacking one hydrogen.

[0027] Nitrogen-mediated polymerization (NMP) Step a) of the method of the present disclosure relates to forming a functionalized polyacrylate via nitroxide-mediated polymerization. Specifically, step a) of the method relates to carrying out nitroxide-mediated polymerization (NMP) by combining an acrylate monomer and a nitroxide initiator in an NMP material, thereby forming a nitroxide polymer initiator. Suitable techniques for NMP polymerization for step a) include, for example, the techniques described in "J.Am.Chem.Soc," Vol. 121, pp. 3904-3920 (1999) and U.S. Patent No. 4,581,429, which are incorporated herein by reference.

[0028] In a particular embodiment, the acrylate monomer in step a) has formula (III), [ka] In the formula, R1 is a C1-C30 hydrocarbyl group.

[0029] In certain embodiments, R1 is a C1-C30 hydrocarbyl group that can be linear, branched, or cyclic. In further embodiments, R1 is a C1-C30 alkyl group that can 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.

[0030] In a particular embodiment, the nitroxide initiator has formula (IV): [ka] Z represents a group having at least one carbon atom, as well as a free radical Z derived from Z. * This is a compound that can initiate polymerization of the acrylate monomer of formula (III) by free radical polymerization, and in which case the radical functional group is present on a carbon atom; R16, R15, R12, and R11 represent the same or different linear or branched substituted or unsubstituted alkyl groups that have a chain length sufficient to cause steric hindrance and weakening of the OZ bond of the compound of formula (IV); and, R14 and R13 represent the same or different linear or branched substituted alkyl groups, or R14CNCR13 may be part of a cyclic structure that can condense with another saturated or aromatic ring, and the cyclic structure or aromatic ring is optionally substituted.

[0031] Examples of nitroxide initiators of formula (IV) include, but are not limited to, those disclosed in U.S. Patent No. 4,581,429, which are incorporated herein by reference.

[0032] In a particular embodiment, the nitroxide polymer initiator formed in step a) has formula (V): [ka] Z represents a group having at least one carbon atom, as well as a free radical Z derived from Z. * This is a compound that can initiate polymerization of the acrylate monomer of formula (III) by free radical polymerization, and in which case the radical functional group is present on a carbon atom; R16, R15, R12, and R11 represent the same or different linear or branched substituted or unsubstituted alkyl groups that have a chain length sufficient to cause steric hindrance and weakening of the OZ bond in the compound of formula (IV); R14 and R13 represent the same or different linear or branched substituted alkyl groups, or R14CNCR13 may be part of a cyclic structure that can condense with another saturated or aromatic ring, and the cyclic structure or aromatic ring is optionally substituted; R1 is a C1-C30 hydrocarbyl group; and, n is between 2 and 500.

[0033] R1 of the nitroxide polymer initiator of formula (V) is the same as R1 of the acrylate monomer of formula (III) (and may be any embodiment of the acrylate monomer of formula (III)).

[0034] In certain embodiments, step a) of the method may be carried out in a neat state. In further embodiments, the NMP material in step a) of the method further comprises a solvent such as a hydrocarbon solvent.

[0035] In certain embodiments, step a) of the method is carried out at a temperature high enough to generate active nitroxide radicals. For example, but not limited to, step a) of the method may be carried out at a temperature of 100 to 150°C.

[0036] End capping Step b) of this method involves end-capping a functionalized polyacrylate using an alpha-substituted acrylate such as alpha-(alkyl)acrylate or alpha-(polymeric)acrylate to form an olefin-acrylate diblock copolymer. Specifically, step b) of this method involves combining an end-capping reaction material containing the alpha-substituted acrylate of formula (V) and a nitroxide polymer initiator to form an olefin-acrylate diblock copolymer.

[0037] 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; and, R1 is a C1-C30 hydrocarbyl group.

[0038] R1 may be any of the embodiments described above.

[0039] In certain embodiments, R is a C1-C26 hydrocarbyl group. In embodiments where R is a C1-C26 hydrocarbyl group, R can be a C1-C26 alkyl group that may be linear, branched, or cyclic. For example, R may 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.

[0040] In further embodiments, R is a polyolefinic group. In certain embodiments, R is a polyolefinic group that can be defined by the properties of RH, where RH has a number average molecular weight greater than 365 g / mol. In further embodiments, R is a polyolefinic group that can be defined by the properties of RH, where 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.

[0041] In further embodiments, R is a polyolefinic group that 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.

[0042] 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.

[0043] In further embodiments, R is a polyolefinic group that can be defined by the properties of RH, and RH has a number-average molecular weight distribution (Mw / Mn or PDI) of 1-10, or 1-7, or 1-5, or 2-4.

[0044] In certain embodiments, R is an ethylene homopolymeric group containing units derived from ethylene.

[0045] In certain embodiments, R is an ethylene / alpha-olefin interpolymer 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.

[0046] In certain embodiments, R is an ethylene / alpha-olefin copolymer group comprising 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.

[0047] In certain embodiments, R is an ethylene / alpha-olefin multiblock interpolymer or olefin block copolymer group as defined herein.

[0048] In further embodiments, R is a polymeryl group of a block complex as defined herein, a specific block complex, or a crystalline block complex.

[0049] In certain embodiments, R is a propylene homopolymeric group containing units derived from propylene.

[0050] In certain embodiments, R is a propylene / alpha-olefin interpolymer 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.

[0051] 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.

[0052] The alpha-substituted acrylate of formula (II) can be prepared by any 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 R3A1 (wherein R is as defined herein). In such non-limiting methods, a nucleophilic substitution reaction occurs, thereby replacing the halogen with a leaving group, R of the organometallic compound of formula R2Zn or R3A1.

[0053] In a particular embodiment, the olefin-acrylate diblock copolymer obtained by this method has formula (VI). [ka]

[0054] Clearly, Z, R, R1, R11-R16, and n of the olefin-acrylate diblock copolymer of formula (VI) are as defined above in relation to steps a) and b) of the present method.

[0055] In certain embodiments, step b) of the method may be carried out in a neat state. In further embodiments, the end-capping reaction material in step b) of the method further comprises a solvent such as a hydrocarbon solvent.

[0056] In certain embodiments, step (b) of the method is carried out at a temperature high enough to generate active nitroxide radicals. For example, but not limited to, step (c) of the method may be carried out at a temperature of 100 to 150°C.

[0057] This method may be described, but is not limited to the following scheme; "controlled radical polymerization" refers to nitroxide-mediated polymerization as described above. [ka]

[0058] Specific embodiments of this disclosure include, but are not limited to, the following: 1. A method for preparing an olefin-acrylate diblock copolymer, the following: a) Performing NMP by combining acrylate monomers and nitroxide initiators in a nitroxide-mediated polymerization (NMP) material, thereby forming a nitroxide polymer initiator, b) Combining end-capping reaction materials containing alpha-substituted acrylates and nitroxide polymer initiators, thereby forming olefin-acrylate diblock copolymers, Methods that include... 2. The alpha-substituted acrylate has formula (II), [ka] The acrylate monomer has formula (III), [ka] The nitroxide initiator has formula (IV), [ka] A nitroxide polymer initiator has formula (V), [ka] The olefin-acrylate diblock copolymer has formula (VI), [ka] Each R1 is independently a C1-C30 hydrocarbyl group; Each R is independently a C1-C26 hydrocarbyl group or a polyolefinyl group; Each Z independently represents a group having at least one carbon atom, and a free radical Z derived from Z can initiate polymerization of the acrylate monomer of formula (III) by free radical polymerization, and the radical functional group is present on a carbon atom; Each of R16, R15, R12, and R11 represents the same or different linear or branched substituted or unsubstituted alkyl group having a chain length sufficient to cause steric hindrance and weakening of the OZ bond in the compound of formula (IV); Each R14 and R13 may represent the same or different linear or branched substituted alkyl group, or R14CNCR13 may be part of a cyclic structure that can condense with another saturated or aromatic ring, and the cyclic structure or aromatic ring may be optionally substituted; and, The method according to Embodiment 1, wherein n is between 2 and 500. 3. The method according to any one of Embodiments 1 to 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-C26 hydrocarbyl group. 5. The method according to Embodiment 4, wherein each R is independently a linear, branched, or cyclic C1-C30, 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 homopolymeryl group containing a unit derived from ethylene. 9. The method according to Embodiment 7, wherein the polyolefin group is an ethylene / alpha-olefin interpolymer 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 copolymer 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 polyolefinyl 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 polyolefinyl 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. The method according to Embodiment 14, wherein the polyolefin group is a propylene / alpha-olefin interpolymeryl group containing 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 polyolefin 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 1 to 23, wherein each of steps a) and b) is carried out at a temperature of 100°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 R3A1, wherein the alpha-(halomethyl)acrylate has formula (I): During the ceremony, [ka] X is a halogen. The method according to any one of Embodiments 1 to 25.

[0059] Test method density: The density is measured according to Method B of ASTM D-792. Melt Index

[0060] The melt index (I2) is measured under conditions of 190°C / 2.16 kg in accordance with ASTM D-1238, which is incorporated herein by reference in its entirety, and reported as grams eluted per 10 minutes. GPC

[0061] The properties of the sample polymers were tested via GPC according to the following procedure.

[0062] 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.

[0063] Calibration of the GPC column set was performed 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 the individual molecular weights were arranged in six "cocktail" mixtures with intervals of at least one order of magnitude.

[0064] 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 grams in 50 mL of solvent for molecular weights of 1,000,000 g / mol or more, and 0.05 grams 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 criterion calibrations for polyethylene molecular weight and polyethylene intrinsic viscosity as functions of the elution column.

[0065] 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., Vol. 6, p. 621 (1968)):

number

[0066] Here, the value of B is 1.0, and the experimentally determined value of A is approximately 0.41.

[0067] 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.

[0068] The number-average, weight-average, and z-average molecular weights were calculated according to the following formula:

number

[0069] 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.

[0070] MWD was expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn).

[0071] The precise A value was determined by adjusting the A value in equation (1) until the Mw and corresponding retention-deposit polynomial calculated using equation (3) matched the known Mw value of 120,000 g / mol for the standard linear polyethylene homopolymer reference.

[0072] 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 instruments include Polymer Laboratories (Shropshire, UK) Model 210 and Model 220). Additional detectors could include a Polymer ChAR (Valencia, Spain), a Precision Detectors (Amherst, Mass.) 2-angle laser light scattering detector Model 2040, and an IR4 infrared detector from a Viscotek (Houston, Tex.) 150R 4-capillary solution viscometer. A GPC with 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 15° or 90° of the light scattering detector was used for calculations.

[0073] Data acquisition was performed using Viscotek TriSEC software, Version 3, and a 4-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 concentration of 0.1 grams of polymer in 50 ml of solvent. Both the chromatographic solvent and the 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 (4h). The injection volume was 200 microliters (μL). The flow rate through the GPC was set to 1 ml / min.

[0074] NMR ( 13 C and 1 H): NMR analysis was performed at room temperature using standard NMR solvents such as chloroform or benzene, and data were acquired using a Varian 500 MHz spectrometer.

[0075] 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 to mitigate any artifacts due to thermal convection. Generally, 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. [4] D was quantified using the Stejskal-Tanner equation (Equation 1), where I and I0 represent the NMR signal intensity with / without a gradient, 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. With the understanding 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 either elute early or delayed / resolved, or vice versa. Therefore, the measurement is performed when the polymer backbone is D 末端 vs D 骨格 By comparing these, explicit intermolecular information is provided to determine whether or not a particular terminal group is capped.

number

[0076] 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]

[0077] 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 these claims.

[0078] Unless otherwise specified, all materials and reagents are commercially available from, for example, Sigma-Aldrich.

[0079] Example 1 [ka] The reaction in Example 1 was carried out under the exemplary and non-limiting reaction scheme described above, in an inert nitrogen atmosphere glove box. 5.88 mL of 0.30 M dioctildin 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 dioctildin solution. During the slow addition process, 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 NMR internal standard. The NMR conversion rate was calculated to be 62.6%. The NMR analysis is shown in Figures 1A and 1B. GC-MS of the reaction aliquots showed the formation of the desired product (lower retention time peaks correspond to Isopar® E). The reaction mixture was quenched with water. Purification and internal standardization to remove Zn salts were performed by column chromatography eluting with 2% ethyl acetate in a hexane mixture. 405 mg of the product was isolated (51%). Example 2 [ka]

[0080] The reaction was carried out in a nitrogen-atmosphere glove box using the NMP procedure described in "J.Am.Chem.Soc.", Vol. 121, pp. 3904-3920 (1999). The inhibitor was removed by passing t-butyl acrylate through an alumina cartridge. The universal initiator 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitrooxide (0.150 g, 0.461 mmol), the corresponding nitroxide (0.005 g, 0.023 mmol, 0.05 equivalents), and t-butyl acrylate (3.4 mL, 23.424 mmol, 50.8 equivalents) were added to a 20 mL vial equipped with a stirring bar. The initial sample was removed. Polymerization was initiated by heating the reaction mixture to 125 °C. After NMR showed a monomer conversion rate of 50% (16 hours), polymerization was quenched by rapidly immersing the vial in liquid nitrogen. The reaction mixture was dissolved in THF and precipitated in water / MeOH (v:v / 1:4) to obtain poly(t-butyl acrylate) as a white solid. GPC (before end capping): Mw=5462, Mn=4650, and PDI=1.18.

[0081] For end capping, the polymer was returned to the glove box and dissolved in approximately 3 mL of toluene. The polymer was degassed by stirring the toluene solution for 10 minutes with the cap removed from the vial. After adding the end cap, the reaction was heated to 125°C. After 96 hours, the reaction appeared to be complete based on the disappearance of protons in the vinyl region and the corresponding disappearance of methine protons at 4.20 ppm. The vial was removed from the heat block and redissolved in 20 mL of THF. The solution was passed through an alumina plug, the solvent was removed from the polymer on a rotovap, and the polymer was recovered by washing several times with chlorobenzene to remove residual toluene and THF, and vacuum drying overnight at 70°C. GPC (after end capping): Mw=6228, Mn=4736, and PDI=internal standard 1.32. The present invention may include the following embodiments. [1] A method for preparing an olefin-acrylate diblock copolymer, the following: a) Performing NMP by combining acrylate monomers and nitroxide initiators in a nitroxide-mediated polymerization (NMP) material, thereby forming a nitroxide polymer initiator, b) Combining an end-capping reaction material containing an alpha-substituted acrylate and the nitroxide polymer initiator, thereby forming the olefin-acrylate diblock copolymer, Methods that include... [2] The alpha-substituted acrylate has formula (II),

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Claims

1. A method for preparing an olefin-acrylate diblock copolymer, the following: a) Performing nitroxide-mediated polymerization (NMP) by combining an acrylate monomer and a nitroxide initiator consisting of 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitrooxide to form a nitroxide polymer initiator derived from the 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitrooxide, b) Combining an end-capping reaction material containing an alpha-substituted acrylate and the nitroxide polymer initiator, thereby forming an olefin-acrylate diblock copolymer derived from the nitroxide polymer initiator, The alpha-substituted acrylate comprises the structure of formula (II): 【Chemistry 1】 In the formula, R is a C1-C26 hydrocarbyl group or a polyolefinyl group; and, The method is such that R1 is a C1-C30 hydrocarbyl group.

2. The method according to claim 1, wherein each of steps a) and b) is carried out at a temperature of 100°C to 150°C.

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