Method for preparing olefin-acrylate block copolymers by RAFT polymerization

Abstract

The present disclosure relates to a method for preparing an olefin-acrylate block copolymer, the method comprising: a) performing reversible addition-fragmentation chain transfer (RAFT) polymerization by combining a RAFT material including an acrylate monomer, a free radical initiator, and a RAFT agent, thereby forming a macroinitiator; and b) combining a reaction material including an α-substituted acrylate, a free radical initiator, and a macroinitiator, thereby forming an olefin-acrylate block copolymer.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 018292, filed on April 30, 2020, which is incorporated herein by reference in its entirety. Background Art

[0003] The present disclosure relates to a method for synthesizing olefin-acrylate block copolymers using reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylate monomers to prepare functionalized polyacrylates, which are subsequently reacted with α-substituted acrylate monomers (such as α-(alkyl)acrylate monomers or α-(polymer-based)acrylate monomers). During the method, α-substituted acrylate monomers suitable for reaction using standard RAFT methods known in the art are used as monomers to react with the polyacrylate produced by RAFT to form olefin-acrylate block copolymers. The method and the resulting olefin-acrylate block copolymers have not been realized until the present disclosure. Summary of the invention

[0004] The present disclosure relates to a method for preparing an olefin-acrylate block copolymer, the method comprising:

[0005] a) performing reversible addition-fragmentation chain transfer (RAFT) polymerization by combining a RAFT material comprising an acrylate monomer, a free radical initiator, and a RAFT agent, thereby forming a macroinitiator; and

[0006] b) combining reactive materials including an alpha-substituted acrylate, a free radical initiator, and a macroinitiator, thereby forming an olefin-acrylate block copolymer.

[0007] The present disclosure further relates to olefin-acrylate block copolymers prepared by the process of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1A and Figure 1B Provide respectively embodiment 1 1 H NMR and 13 C NMR spectroscopy.

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

[0010] Figure 2A and Figure 2B Provide respectively embodiment 2 1 H NMR and diffusion NMR spectroscopy. DETAILED DESCRIPTION

[0011] definition

[0012] All references herein to the Periodic Table of the Elements shall refer to the Periodic Table published and copyrighted by CRC Press, Inc. in 2003. Furthermore, any reference to one or more Groups shall be to the Group or Groups reflected in such Periodic Table using the IUPAC system for numbering the Groups.

[0013] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are by weight.

[0014] For purposes of U.S. patent practice, any patent, patent application, or publication mentioned herein is hereby incorporated by reference in its entirety (or its equivalent U.S. version is so incorporated by reference), especially with respect to disclosure of synthetic techniques, definitions (to the extent inconsistent with any definitions provided herein), and general knowledge in the art.

[0015] Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit, and include the lower limit and the upper limit. For ranges containing exact values ​​(e.g., 1 or 2; or 3 to 5; or 6; or 7), any subranges between any two exact values ​​are included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6, etc.). Numerical ranges disclosed herein further include fractions between any two exact values.

[0016] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not the components, steps, or procedures are specifically disclosed. Conversely, the term "consisting essentially of excludes any other components, steps, or procedures from the scope of any subsequent listing, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically recited or listed. Unless otherwise stated, the term "or" refers to the listed members individually and in any combination.

[0017] As used herein, the term "hydrocarbyl", "alkyl" and similar terms refer to compounds composed entirely of hydrogen and carbon, including aliphatic, aromatic, acyclic, cyclic, polycyclic, branched, unbranched, saturated and unsaturated compounds. The term "hydrocarbyl", "hydrocarbyl group", "alkyl", "alkyl group", "aryl", "aryl group" and similar terms are intended to include every possible isomer, including every structural isomer or stereoisomer.

[0018] The term "cyclic" refers to a series of atoms in a polymer or compound, wherein such series comprises one or more rings. Thus, the term "cyclic hydrocarbon group" refers to a hydrocarbon group containing one or more rings. As used herein, a "cyclic hydrocarbon group" may contain a non-cyclic (straight or branched) portion in addition to one or more rings.

[0019] The term "polymer" refers to a compound prepared by reacting (i.e., polymerizing) a set of monomers, wherein the set of monomers is either a homogeneous (i.e., only one type) set of monomers or a heterogeneous (i.e., more than one type) set of monomers. The term polymer as used herein includes the term "homopolymer," which refers to a polymer prepared from a homogeneous set of monomers, and the term "interpolymer" as defined below.

[0020] "Interpolymer" refers to an A polymer prepared by polymerizing at least two different types of monomers. This term encompasses "copolymers," i.e., polymers prepared from two different types of monomers, and polymers prepared from more than two different types of monomers, such as terpolymers, tetrapolymers, etc. This term also includes all forms of interpolymers, such as random, block, homogeneous, heterogeneous, etc.

[0021] "Polyolefin" is a polymer produced by the polymerization of olefins as monomers, wherein the olefin monomer is a linear, branched or cyclic compound of carbon and hydrogen having at least one double bond. Thus, the term "polyolefin" as used herein includes and encompasses the terms "ethylene polymer", "propylene-based polymer", "ethylene homopolymer", "propylene homopolymer", "ethylene / α-olefin interpolymer", "ethylene / α-olefin copolymer", "ethylene / α-olefin multi-block interpolymer", "block composite", "specified block composite", "crystalline block composite" and "propylene / α-olefin interpolymer" and "propylene / α-olefin copolymer".

[0022] "Ethylene polymers" are polymers that contain a majority amount of polymerized ethylene, based on the weight of the polymer, and optionally may further contain polymerized units of at least one comonomer. "Ethylene interpolymers" are interpolymers that contain, in polymerized form, a majority amount of ethylene, based on the weight of the interpolymer, and further contain polymerized units of at least one comonomer. "Ethylene homopolymers" are polymers that include repeating units derived from ethylene, but do not exclude residual amounts of other components.

[0023] As used herein, the term "ethylene / α-olefin interpolymer" refers to a polymer that contains, in polymerized form, a majority weight percent of ethylene (based on the weight of the interpolymer) and at least one comonomer that is an α-olefin. The ethylene / α-olefin interpolymer can be a random or block interpolymer. The term "ethylene / α-olefin interpolymer" encompasses the terms "ethylene / α-olefin copolymer" and "ethylene / α-olefin multi-block interpolymer".

[0024] As used herein, the term "ethylene / α-olefin copolymer" refers to a copolymer comprising, in polymerized form, a majority weight percent of ethylene (based on the weight of the copolymer) and a comonomer as an α-olefin, wherein ethylene and the α-olefin are the only two monomer types. The ethylene / α-olefin copolymer may be a random or block copolymer.

[0025] As used herein, the term "ethylene / α-olefin multi-block interpolymer" or "olefin block copolymer" refers to an interpolymer comprising ethylene and one or more copolymerizable α-olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more (preferably three or more) polymerized monomer units, said blocks or segments differing in chemical or physical properties. Specifically, the term refers to a polymer comprising two or more (preferably three or more) chemically distinct regions or segments (referred to as "blocks") joined in a linear manner rather than in a pendant or grafted manner, i.e., a polymer comprising chemically distinct units joined (covalently bonded) end-to-end with respect to polymerized functional groups. The blocks differ in the amount or type of comonomer incorporated therein, density, amount of crystallinity, type of crystallinity (e.g., polyethylene versus polypropylene), crystallite size attributable to polymers of such composition, type or degree of tacticity (isotactic or syndiotactic), regioregularity or regioirregularity, amount of branching (including long chain branching or hyperbranching), uniformity, and / or any other chemical or physical property. Block copolymers are characterized by unique distributions of both polymer polydispersity (PDI or Mw / Mn) and block length distribution, for example, based on the effect of using one or more shuttling agents in combination with a catalyst system. Non-limiting examples of the disclosed olefin block copolymers and methods for making the same are disclosed in U.S. Pat. Nos. 7,858,706 B2, 8,198,374 B2, 8,318,864 B2, 8,609,779 B2, 8,710,143 B2, 8,785,551 B2, and 9,243,090 B2, all of which are incorporated herein by reference in their entirety.

[0026] The term "block composite" ("BC") refers to a polymer comprising three polymer components: (i) a vinyl polymer (EP) having an ethylene content of 10 mol% to 90 mol% based on the total moles of polymerized monomer units in the vinyl polymer (EP) (soft copolymer); (ii) an α-olefin-based polymer (AOP) having an α-olefin content greater than 90 mol% based on the total moles of polymerized monomer units in the α-olefin-based polymer (AOP) (hard copolymer); and (iii) a block copolymer having an ethylene block (EB) and an α-olefin block (AOB) (diblock copolymer); wherein the ethylene block of the block copolymer has the same composition as the EP of component (i) of the block composite, and the α-olefin block of the block copolymer has the same composition as the AOP of component (ii) of the block composite. In addition, in the block composite, the composition split between the amounts of EP and AOP will be substantially the same as the composition split between the corresponding blocks in the block copolymer. Non-limiting examples of block composites of the present disclosure and methods for making the same are disclosed in U.S. Pat. Nos. 8,686,087 and 8,716,400, which are incorporated herein by reference in their entirety.

[0027] The term "specified block composite" ("SBC") refers to a polymer comprising three polymer components: (i) a vinyl polymer (EP) having an ethylene content of 78 mol% to 90 mol% based on the total moles of polymerized monomer units in the vinyl polymer (EP) (soft copolymer); (ii) an α-olefin-based polymer (AOP) having an α-olefin content of 61 mol% to 90 mol% based on the total moles of polymerized monomer units in the α-olefin-based polymer (AOP) (hard copolymer); and (iii) a block copolymer having an ethylene block (EB) and an α-olefin block (AOB) (diblock copolymer); wherein the ethylene block of the block copolymer has the same composition as the EP of component (i) of the specified block composite, and the α-olefin block of the block copolymer has the same composition as the AOP of component (ii) of the specified block composite. In addition, in the specified block composite, the composition split between the amounts of EP and AOP will be substantially the same as the composition split between the corresponding blocks in the block copolymer. Non-limiting examples of designated block composites of the present disclosure and methods for preparing the same are disclosed in WO 2017 / 044547, which is incorporated herein by reference in its entirety.

[0028] The term "crystalline block composite" ("CBC") refers to a polymer comprising three components: (i) a crystalline vinyl polymer (CEP) having an ethylene content greater than 90 mol% based on the total moles of polymerized monomer units in the crystalline vinyl polymer (CEP); (ii) a crystalline α-olefin-based polymer (CAOP) having an α-olefin content greater than 90 mol% based on the total moles of polymerized monomer units in the crystalline α-olefin-based copolymer (CAOP); and (iii) a block copolymer comprising a crystalline ethylene block (CEB) and a crystalline α-olefin block (CAOB); wherein the CEB of the block copolymer is the same composition as the CEP of component (i) of the crystalline block composite, and the CAOB of the block copolymer is the same composition as the CAOP of component (ii) of the crystalline block composite. In addition, in the crystalline block composite, the composition split between the amounts of CEP and CAOP will be substantially the same as the composition split between the corresponding blocks in the block copolymer. Non-limiting examples of the crystalline block composites of the present disclosure and methods for preparing the same are disclosed in U.S. Pat. No. 8,822,598 B2 and WO 2016 / 01028961 A1, which are incorporated herein by reference in their entirety.

[0029] "Propylene-based polymers" are polymers that contain a majority amount of polymerized propylene, based on the weight of the polymer, and optionally may further contain polymerized units of at least one comonomer. "Propylene-based interpolymers" are interpolymers that contain, in polymerized form, a majority amount of propylene, based on the weight of the interpolymer, and further contain polymerized units of at least one comonomer. "Propylene homopolymers" are polymers that include repeating units derived from propylene, but do not exclude residual amounts of other components.

[0030] As used herein, the term "propylene / α-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 α-olefin (wherein ethylene is considered an α-olefin). The propylene / α-olefin interpolymer can be a random or block interpolymer. The term "propylene / α-olefin interpolymer" includes the term "propylene / α-olefin copolymer".

[0031] As used herein, the term "propylene / α-olefin copolymer" refers to a copolymer comprising, in polymerized form, a majority weight percent of propylene (based on the weight of the copolymer) and a comonomer as an α-olefin, wherein propylene and the α-olefin are the only two monomer types. The propylene / α-olefin copolymer may be a random or block copolymer.

[0032] The terms "polymeryl," "polymeryl group," and similar terms refer to a polymer lacking one hydrogen.

[0033] The terms "polyolefinyl", "polyolefinyl group" and similar terms refer to a polyolefin lacking one hydrogen.

[0034] RAFT polymerization

[0035] Step a) of the method of the present disclosure involves forming a functionalized polyacrylate by reversible addition-fragmentation chain transfer (RAFT) polymerization. Specifically, step a) of the method of the present invention involves RAFT polymerization by combining a RAFT material including an acrylate monomer, a free radical initiator, and a RAFT agent, thereby forming a macroinitiator. Techniques and conditions suitable for RAFT polymerization in step a) are known in the art and include, for example, those described in U.S. Pat. Nos. 6,747,111 and WO 98 / 01478, which are incorporated herein by reference.

[0036] In certain embodiments, the acrylate monomer of step a) has formula (III):

[0037] wherein R1 is hydrogen or a C1-C30 hydrocarbon group, and R2 is hydrogen or a methyl group.

[0038] In certain embodiments, R1 is a C1-C30 hydrocarbon group which may be linear, branched or cyclic. In other embodiments, R1 is a C1-C30 alkyl group which may be linear, branched or cyclic. For example, R1 may be a linear, 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.

[0039] In certain embodiments, the RAFT agent has formula (IV):

[0040] in:

[0041] R11 is selected from the group consisting of: optionally substituted alkyl; optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic ring; optionally substituted alkylthio; optionally substituted alkoxy; and optionally substituted dialkylamino; and wherein R11 is a free radical leaving group capable of initiating free radical polymerization;

[0042] Z is selected from the group consisting of hydrogen, chlorine, optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl (-COOR"), carboxyl (-COOH), optionally substituted acyloxy (-O2CR"), optionally substituted carbamoyl (-CONR"2), cyano (-CN), dialkyl or diaryl-phosphonic acid [-P(=O)OR"2], and dialkyl or diaryl-phosphonic acid [-P(=O)R"2]; and

[0043] R" is selected from the group consisting of: optionally substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclic, aralkyl, alkaryl, wherein the substituents are independently selected from the group consisting of: epoxy, hydroxy, alkoxyacyl, acyloxy, carboxyl (and salts), sulfonic acid (and salts), alkoxy or aryloxycarbonyl, isocyanato, cyano, silyl, halide and dialkylamino.

[0044] Examples of RAFT agents of formula (IV) include, but are not limited to, those disclosed in US Pat. No. 6,747,111 B2 and WO 98 / 01478.

[0045] Free radical initiators are sources of free radicals. Suitable free radical initiators of the present disclosure are compounds that provide free radicals that add to monomers to produce propagating free radicals. Propagating free radicals are free radical species that have added one or more monomer units and are capable of adding more monomer units.

[0046] The source of the initiating free radicals can be any suitable method of generating free radicals that provide free radicals for addition to the monomer to generate propagating free radicals. This includes sources such as thermal homolysis of one or more suitable compounds (such as peroxides, peroxyesters or azo compounds), spontaneous generation from monomers, redox initiation systems and photochemical initiation systems, or high energy radiation (such as electron beams, X-radiation or gamma radiation). The initiation system is selected so that under the reaction conditions, the initiator or initiating free radical has no substantial adverse interaction with the transfer agent under the experimental conditions. The initiator should also have the necessary solubility in the reaction medium or monomer mixture.

[0047] Examples of suitable free radical initiators for use in the present disclosure include azo compounds and peroxides, such as: 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-cyano-2-butane), dimethyl 2,2'-azobis(methyl isobutyrate), 4,4'-azobis(4-cyanovaleric acid), 4,4'-azobis(4-cyanopentan-1-ol), 1,1'-azobis(cyclohexanecarbonitrile), 2-(tert-butylazo) )-2-cyanopropane, 2,2'-azobis[2-methyl-N-(1,1)-bis(hydroxymethyl)-2-hydroxyethyl]propionamide, 2,2'-azobis[2-methyl-N-hydroxyethyl)]-propionamide, 2,2'-azobis(N,N'-dimethyleneisobutylamidine) dihydrochloride, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis(N,N'-dimethyleneisobutylamine), 2, 2'-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)2-hydroxyethyl]propionamide), 2,2'-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide), 2,2'-azobis[2-methyl-N(2-hydroxyethyl)propionamide], 2,2'-azobis(isobutylamide) dihydrate, 2,2'-azobis(2,2,4-trimethylpentane), 2,2'-azobis (2-methylpropane), tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyoctanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxyisobutyrate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide, dibenzoyl peroxide, dodecyl peroxide, potassium persulfate, ammonium persulfate, di-tert-butyl subnitrite or dicumyl subnitrite.

[0048] Free radicals may also be generated thermally from monomers, photochemically, from redox initiation systems, or by a combination of these methods. Photochemical initiator systems are selected to have the necessary solubility in the reaction medium or monomer mixture and a suitable quantum yield for free radical generation under the conditions of polymerization. Examples include benzoin derivatives, benzophenones, acylphosphine oxides, and photoredox systems. Redox initiator systems are selected to have the necessary solubility in the reaction medium or monomer mixture and a suitable rate of free radical generation under the conditions of polymerization; these initiation systems may include combinations of the following oxidants and reductants:

[0049] Oxidants: potassium peroxodisulfate, hydrogen peroxide, tert-butyl hydroperoxide.

[0050] Reducing agents: iron (II), titanium (III), potassium thiosulfate, potassium bisulfite.

[0051] Other suitable initiation systems are described elsewhere in the literature. See, for example, Moad and Solomon, The Chemistry of Free Radical Polymerization, Guymon Publishing, London, 1995, pp. 53-95.

[0052] In certain embodiments, the macroinitiator formed in step a) has formula (V):

[0053] in:

[0054] R1 is hydrogen or a C1-C30 hydrocarbon group;

[0055] R2 is hydrogen or a methyl group;

[0056] Z is selected from the group consisting of hydrogen, chlorine, optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl (-COOR"), carboxyl (-COOH), optionally substituted acyloxy (-O2CR"), optionally substituted carbamoyl (-CONR"2), cyano (-CN), dialkyl or diaryl-phosphonic acid [-P(=O)OR"2], and dialkyl or diaryl-phosphonic acid [-P(=O)R"2];

[0057] R" is selected from the group consisting of: optionally substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclic, aralkyl, alkaryl, wherein the substituents are independently selected from the group consisting of: epoxy, hydroxy, alkoxyacyl, acyloxy, carboxyl (and salts), sulfonic acid (and salts), alkoxy or aryloxycarbonyl, isocyanato, cyano, silyl, halide and dialkylamino;

[0058] I is a free radical initiator or a free radical leaving group derived from R11 of a RAFT agent that initiates free radical polymerization; and

[0059] n is 2 to 500.

[0060] R1 of the macroinitiator of formula (V) is the same as R1 of the acrylate monomer of formula (III) (and may be any embodiment thereof).

[0061] In certain embodiments, step a) of the method of the present invention may be performed simply. In other embodiments, the RAFT material in step a) of the method of the present invention further comprises a solvent, such as a hydrocarbon solvent.

[0062] In certain embodiments, step a) of the method of the present invention is carried out at a temperature suitable for RAFT polymerization. For example, but not limited to, step a) of the method of the present invention can be carried out at a temperature of 40°C to 150°C.

[0063] The amount and proportion of RAFT material in step a) may be adjustable and will be known to those skilled in the art.

[0064] Reaction with α-substituted acrylates

[0065] 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 including an α-substituted acrylate, a free radical initiator, and a macroinitiator of formula (V), thereby forming an olefin-acrylate block copolymer.

[0066] In certain embodiments, the α-substituted acrylate has formula (II):

[0067]

[0068] wherein R is a C1-C26 hydrocarbon group or a polyolefin group; and

[0069] R1 is hydrogen or a C1-C30 hydrocarbon group.

[0070] R1 may be any of the embodiments described above.

[0071] In certain embodiments, R is a C1-C26 hydrocarbyl group. In embodiments where R is a C1-C26 hydrocarbyl group, R may 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 comprising 1 to 26 carbon atoms, or 1 to 10 carbon atoms, or 1 to 8 carbon atoms.

[0072] In other embodiments, R is a polyolefin-based group. In certain embodiments, R is a polyolefin-based group, which can be defined by the properties of RH, wherein the number average molecular weight of RH is greater than 365 g / mol. In other embodiments, R is a polyolefin-based group, which can 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.

[0073] In other embodiments, R is a polyolefin-based group, which can be defined by the nature of RH, wherein the density of RH is from 0.850 g / cc to 0.965 g / cc, or from 0.860 g / cc to 0.950 g / cc, or from 0.865 g / cc to 0.925 g / cc.

[0074] In another embodiment, R is a polyolefin-based group, which can be defined by the properties of RH, wherein the melt index (I2) of RH is from 0.01 g / 10 min to 2,000 g / 10 min, or from 0.01 g / 10 min to 1,500 g / 10 min, or from 0.1 g / 10 min to 1,000 g / 10 min, or from 0.1 g / 10 min to 500 g / 10 min, or from 0.1 g / 10 min to 100 g / 10 min.

[0075] In other embodiments, R is a polyolefin-based group, which can be defined by the nature of RH, wherein the number average molecular weight distribution (Mw / Mn or PDI) of RH is 1 to 10 or 1 to 7 or 1 to 5 or 2 to 4.

[0076] In certain embodiments, R is an ethylene homopolymer-based group comprising units derived from ethylene.

[0077] In certain embodiments, R is an ethylene / α-olefin interpolymer group comprising units derived from ethylene and at least one C3-C30 α-olefin. The C3-C30 α-olefin can be, for example, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene.

[0078] In certain embodiments, R is an ethylene / α-olefin copolymer group comprising units derived from ethylene and C3-C30 α-olefins. The C3-C30 α-olefins 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.

[0079] In certain embodiments, R is an ethylene / α-olefin multi-block interpolymer-based group or an olefin block copolymer-based group as defined herein.

[0080] In further embodiments, R is a polymer-based group of a block composite, a specific block composite, or a crystalline block composite as defined herein.

[0081] In certain embodiments, R is a propylene homopolymer group comprising units derived from propylene.

[0082] In certain embodiments, R is a propylene / α-olefin interpolymer group comprising units derived from propylene and at least one comonomer that is 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.

[0083] In certain embodiments, R is a propylene / α-olefin copolymer group comprising units derived from propylene and a comonomer that is 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.

[0084] The α-substituted acrylate of formula (II) can be prepared by any suitable method. A non-limiting method for preparing the α-substituted acrylate of formula (II) is a method disclosed in co-pending U.S. Provisional Application Nos. 62 / 954,941 and 62 / 954,956. For example, the α-substituted acrylate of formula (II) can be prepared by combining materials including 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 R of the organometallic compound of formula R2Zn or R3Al.

[0085] In certain embodiments, the resulting olefin-acrylate block copolymer of the process of the present invention has formula (VI):

[0086]

[0087] Obviously, each of R, R1, R2, I, Z and n of the olefin-acrylate block copolymer of formula (VI) is as defined above in conjunction with steps a) and b) of the process of the present invention, and m is from 1 to 50. When m=1, the block copolymer is a linear olefin-acrylate diblock copolymer. When m>1, a comb-like block copolymer is formed.

[0088] In certain embodiments, step b) of the method of the present invention can be simply performed. In other embodiments, the reaction materials in step b) of the method of the present invention further include a solvent, such as a hydrocarbon solvent.

[0089] For example, but not limited to, step c) of the method of the present invention may be carried out at a temperature of 40°C to 150°C.

[0090] The amounts and ratios of the reaction materials in step b) may be adjustable and will be known to those of ordinary skill in the art.

[0091] The method of the present invention can be described by, but not limited to, the following scheme.

[0092]

[0093] Specific embodiments of the present disclosure include but are not limited to the following:

[0094] 1. A method for preparing an olefin-acrylate block copolymer, the method comprising:

[0095] a) performing reversible addition-fragmentation chain transfer (RAFT) by combining a RAFT material comprising an acrylate monomer, a free radical initiator and a RAFT agent, thereby forming a macroinitiator; and

[0096] b) combining reactive materials including an alpha-substituted acrylate, a free radical initiator, and the macroinitiator, thereby forming the olefin-acrylate block copolymer.

[0097] 2. The method according to embodiment 1, wherein:

[0098] The α-substituted acrylate has formula (II):

[0099]

[0100] The acrylate monomer has formula (III):

[0101]

[0102] The RAFT agent has formula (IV):

[0103]

[0104] The macroinitiator has formula (V):

[0105]

[0106] The olefin-acrylate block copolymer has formula (VI):

[0107] And among them:

[0108] Each R1 is independently hydrogen or a C1-C30 hydrocarbon group;

[0109] Each R2 is independently hydrogen or a methyl group;

[0110] Each R is independently a C1-C26 hydrocarbon group or a polyolefin group;

[0111] R11 is selected from the group consisting of: optionally substituted alkyl; optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic ring; optionally substituted alkylthio; optionally substituted alkoxy; and optionally substituted dialkylamino; and wherein R11 is a free radical leaving group capable of initiating free radical polymerization;

[0112] each Z is selected from the group consisting of hydrogen, chlorine, optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl (-COOR"), carboxyl (-COOH), optionally substituted acyloxy (-O2CR"), optionally substituted carbamoyl (-CONR"2), cyano (-CN), dialkyl or diaryl-phosphonic acid [-P(=O)OR"2], and dialkyl or diaryl-phosphonic acid [-P(=O)R"2];

[0113] Each R" is independently selected from the group consisting of: optionally substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclic, aralkyl, alkaryl, wherein the substituents are independently selected from the group consisting of: epoxy, hydroxy, alkoxyacyl, acyloxy, carboxyl (and salts), sulfonic acid (and salts), alkoxy or aryloxycarbonyl, isocyanato, cyano, silyl, halo and dialkylamino;

[0114] Each I· is independently a free radical initiator or a free radical leaving group derived from R11 of a RAFT agent that initiates free radical polymerization;

[0115] each n is 2 to 500, and

[0116] m is 1 to 50.

[0117] 3. The method according to any one of the preceding embodiments, wherein each R1 is independently a linear, branched or cyclic C1-C30 or C1-C10 or C1-C8 alkyl group.

[0118] 4. The method according to any one of the preceding embodiments, wherein each R is independently a C1-C26 hydrocarbon group.

[0119] 5. The method according to embodiment 4, wherein each R is independently a linear, branched or cyclic C1-C26 or C1-C10 or C1-C8 alkyl group.

[0120] 6. The method of any one of embodiments 1 to 3, wherein each R is independently a polyolefin-based group.

[0121] 7. The method according to embodiment 6, wherein the polyolefin-based group is a vinyl polymer-based group.

[0122] 8. A method according to embodiment 7, wherein the polyolefin-based group is an ethylene homopolymer-based group comprising units derived from ethylene.

[0123] 9. The method according to embodiment 7, wherein the polyolefin-based group is an ethylene / α-olefin interpolymer-based group comprising units derived from ethylene and a C3-C30 α-olefin.

[0124] 10. The method according to embodiment 7, wherein the polyolefin-based group is an ethylene / α-olefin copolymer-based group comprising units derived from ethylene and a C3-C30 α-olefin.

[0125] 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.

[0126] 12. The method according to embodiment 7, wherein the polyolefin-based group is an ethylene / α-olefin multi-block interpolymer-based group.

[0127] 13. The method according to embodiment 6, wherein the polyolefin-based group is selected from the group consisting of: polymer-based groups of block composites, specified block composites, and crystalline block composites.

[0128] 14. The method of embodiment 6, wherein the polyolefin-based group is a propylene-based polymer-based group.

[0129] 15. The method according to embodiment 14, wherein the polyolefin-based group is a propylene homopolymer-based group comprising units derived from propylene.

[0130] 16. The method according to embodiment 14, wherein the polyolefin-based group is a propylene / α-olefin interpolymer-based group comprising units derived from propylene and ethylene or a C4-C30 α-olefin.

[0131] 17. The method according to embodiment 14, wherein the polyolefin-based group is a propylene / α-olefin copolymer-based group comprising units derived from propylene and ethylene or a C4-C30 α-olefin.

[0132] 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.

[0133] 19. The method according to any one of embodiments 6 to 18, wherein the polyolefin-based group is definable by the nature of RH, and wherein the number average molecular weight of RH is greater than 365 g / mol.

[0134] 20. The method of any one of embodiments 6 to 19, wherein the polyolefin-based group is defined by the nature of RH, and wherein the number average molecular weight of RH is from greater than 365 g / mol to 10,000,000 g / mol, or from greater than 365 g / mol to 5,000,000 g / mol, or from greater than 365 g / mol to 1,000,000 g / mol, or from greater than 365 g / mol to 750,000 g / mol, or from greater than 365 g / mol to 500,000 g / mol, or from greater than 365 g / mol to 250,000 g / mol.

[0135] 21. The method of any one of embodiments 6 to 20, wherein the polyolefin-based group is definable by the nature of RH, and wherein the density of RH is from 0.850 g / cc to 0.965 g / cc, or from 0.860 g / cc to 0.950 g / cc, or from 0.865 g / cc to 0.925 g / cc.

[0136] 22. The method of any one of embodiments 6 to 21, wherein the polyolefin-based group can be defined by the nature of RH, and wherein the melt index (I2) of RH is from 0.01 g / 10 min to 2,000 g / 10 min, or from 0.01 g / 10 min to 1,500 g / 10 min, or from 0.1 g / 10 min to 1,000 g / 10 min, or from 0.1 g / 10 min to 500 g / 10 min, or from 0.1 g / 10 min to 100 g / 10 min.

[0137] 23. The method of any one of embodiments 6 to 22, wherein the polyolefin-based group is definable by the nature 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.

[0138] 24. The method according to any one of embodiments 2 to 23, wherein m is 1.

[0139] 25. The method according to any one of the preceding embodiments, wherein each of steps a) and b) is performed at a temperature of 40°C to 150°C.

[0140] 26. The method according to any one of the preceding embodiments, wherein the α-substituted acrylate is prepared by a method comprising combining starting materials comprising an α-(halomethyl)acrylate and an organometallic compound of formula R2Zn or R3Al, wherein the α-(halomethyl)acrylate has formula (I):

[0141] in:

[0142] X is a halide, and R and R1 are as defined above.

[0143] 27. The method according to any one of the preceding embodiments, wherein each free radical initiator is an azo compound or a peroxide.

[0144] 28. The method according to any one of the preceding embodiments, wherein the RAFT material and / or the reaction material further comprises a solvent.

[0145] 29. An olefin-acrylate block copolymer having formula (VI):

[0146] And among them:

[0147] Each R1 is independently hydrogen or a C1-C30 hydrocarbon group;

[0148] R2 is hydrogen or a methyl group;

[0149] R is a C1-C26 hydrocarbon group or a polyolefin group;

[0150] R11 is selected from the group consisting of: optionally substituted alkyl; optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic ring; optionally substituted alkylthio; optionally substituted alkoxy; and optionally substituted dialkylamino; and wherein R11 is a free radical leaving group capable of initiating free radical polymerization;

[0151] Z is selected from the group consisting of hydrogen, chlorine, optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl (-COOR"), carboxyl (-COOH), optionally substituted acyloxy (-O2CR"), optionally substituted carbamoyl (-CONR"2), cyano (-CN), dialkyl or diaryl-phosphonic acid [-P(=O)OR"2], and dialkyl or diaryl-phosphonic acid [-P(=O)R"2];

[0152] Each R" is independently selected from the group consisting of: optionally substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclic, aralkyl, alkaryl, wherein the substituents are independently selected from the group consisting of: epoxy, hydroxy, alkoxyacyl, acyloxy, carboxyl (and salts), sulfonic acid (and salts), alkoxy or aryloxycarbonyl, isocyanato, cyano, silyl, halo and dialkylamino;

[0153] I is a free radical initiator or a free radical leaving group obtained from R11 of a RAFT agent that initiates free radical polymerization;

[0154] n is 2 to 500, and

[0155] m is 1 to 50.

[0156] 30. The olefin-acrylate block copolymer according to embodiment 29, wherein each R1 is independently a linear, branched or cyclic C1-C30 or C1-C10 or C1-C8 alkyl group.

[0157] 31. The olefin-acrylate block copolymer according to embodiment 29 or 30, wherein R is a C1-C26 alkyl group.

[0158] 32. The olefin-acrylate block copolymer according to embodiment 31, wherein each R is a linear, branched or cyclic C1-C26 or C1-C10 or C1-C8 alkyl group.

[0159] 33. The olefin-acrylate block copolymer according to embodiment 29 or 30, wherein R is a polyolefin-based group.

[0160] 34. The olefin-acrylate block copolymer according to embodiment 33, wherein the polyolefin-based group is a vinyl polymer-based group.

[0161] 35. The olefin-acrylate block copolymer according to embodiment 34, wherein the polyolefin-based group is an ethylene homopolymer-based group comprising units derived from ethylene.

[0162] 36. The olefin-acrylate block copolymer according to embodiment 34, wherein the polyolefin-based group is an ethylene / α-olefin interpolymer-based group comprising units derived from ethylene and a C3-C30 α-olefin.

[0163] 37. The olefin-acrylate block copolymer according to embodiment 34, wherein the polyolefin-based group is an ethylene / α-olefin copolymer-based group comprising units derived from ethylene and a C3-C30 α-olefin.

[0164] 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.

[0165] 39. The olefin-acrylate block copolymer according to embodiment 34, wherein the polyolefin-based group is an ethylene / α-olefin multi-block interpolymer-based group.

[0166] 40. The olefin-acrylate block copolymer according to embodiment 33, wherein the polyolefin-based group is selected from the group consisting of: polymer-based groups of block composites, specified block composites, and crystalline block composites.

[0167] 41. The olefin-acrylate block copolymer according to embodiment 33, wherein the polyolefin-based group is a propylene-based polymer-based group.

[0168] 42. The olefin-acrylate block copolymer according to embodiment 41, wherein the polyolefin-based group is a propylene homopolymer-based group comprising units derived from propylene.

[0169] 43. The olefin-acrylate block copolymer according to embodiment 41, wherein the polyolefin-based group is a propylene / α-olefin interpolymer group comprising units derived from propylene and ethylene or a C4-C30 α-olefin.

[0170] 44. The olefin-acrylate block copolymer according to embodiment 41, wherein the polyolefin-based group is a propylene / α-olefin copolymer-based group comprising units derived from propylene and ethylene or a C4-C30 α-olefin.

[0171] 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.

[0172] 46. ​​The olefin-acrylate block copolymer according to any one of embodiments 33 to 45, wherein the polyolefin-based group is definable by the nature of RH, and wherein the number average molecular weight of RH is greater than 365 g / mol.

[0173] 47. An olefin-acrylate block copolymer according to any one of embodiments 33 to 46, wherein the polyolefin-based group can be defined by the nature 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.

[0174] 48. The olefin-acrylate block copolymer of any one of embodiments 33 to 47, wherein the polyolefin-based group can be defined by the nature 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.

[0175] Wherein the polyolefin-based 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.

[0176] 49. An olefin-acrylate block copolymer according to any one of embodiments 33 to 48, wherein the polyolefin-based group can be defined by the nature 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.

[0177] 50. The olefin-acrylate block copolymer according to any one of embodiments 33 to 49, wherein m is 1.

[0178] Test Method

[0179] density :

[0180] Density was measured according to ASTM D-792, Method B.

[0181] Melt Index :

[0182] Melt index (I2) is measured according to ASTM D-1238 (incorporated herein by reference in its entirety), Condition 190°C / 2.16 kg, and is reported in grams eluted per 10 minutes.

[0183] GPC

[0184] The properties of the sample polymers were tested by GPC as follows.

[0185] Molecular weight (MW) and molecular weight distribution (MWD) were determined using a high temperature gel permeation chromatography system (GPC IR) consisting of an infrared concentration detector (IR-5) from PolymerChar Inc (Valencia, Spain). The carrier solvent was 1,2,4-trichlorobenzene (TCB). The autosampler chamber was operated at 160°C, and the column chamber was operated at 150°C. The columns used were four Polymer Laboratories Mixed A LS, 20 micron columns. Chromatographic solvent (TCB) and sample preparation solvent were from the same solvent source, with 250ppm of butylated hydroxytoluene (BHT) and nitrogen injection. Samples were prepared at a concentration of 2mg / mL in TCB. The polymer sample was gently shaken for 2 hours at 160°C. The injection volume was 200μl, and the flow rate was 1.0 ml / min.

[0186] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards. The molecular weights of the standards ranged from 580 g / mol to 8,400,000 g / mol and were arranged in 6 "cocktail" mixtures with at least one decade between individual molecular weights.

[0187] The GPC column set was calibrated prior to running the example by running twenty-one narrow molecular weight distribution polystyrene standards. The molecular weight (Mw) range of the standards was from 580 grams per mole (g / mol) to 8,400,000 grams per mole (g / mol), and the standards were contained in 6 "cocktail" mixtures. Each standard mixture was separated by at least one decade between individual molecular weights. The standard mixtures were purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards were prepared as follows: 0.025 g in 50 mL of solvent for molecular weights equal to or greater than 1,000,000 g / mol; and 0.05 g in 50 mL of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards were dissolved by gentle stirring at 80°C for 30 minutes. The narrow standard mixtures were run first, and were run in the order of decreasing the highest molecular weight (Mw) component to minimize degradation. The polystyrene standard peak molecular weight was converted to polyethylene Mw using the Mark-Houwink constants. Once the constants were obtained, these two values ​​were used to construct two linear reference routine calibration values ​​for polyethylene molecular weight and polyethylene intrinsic viscosity as a function of the eluting column.

[0188] Polystyrene standard peak molecular weights were converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0189] M 聚乙烯 =A(M 聚苯乙烯 ) B (1)

[0190] Here the value of B is 1.0, while the experimentally determined value of A is about 0.41.

[0191] The corresponding polyethylene-equivalent calibration points obtained from equation (1) were fit to their observed elution volumes of the polystyrene standards using a third order polynomial.

[0192] The number average molecular weight, weight average molecular weight and z average molecular weight were calculated according to the following equations:

[0193]

[0194]

[0195] Among them, Wf i is the weight fraction of the ith component, and M i is the molecular weight of the ith component.

[0196] MWD is expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn).

[0197] The exact 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 agrees with the known Mw value of 120,000 g / mol for a standard linear polyethylene homopolymer reference.

[0198] The GPC system consisted of a Waters (Milford, Mass.) 150°C high temperature chromatograph equipped with an organic-based differential refractometer (RI) (other suitable high temperature GPC instruments include Polymer Laboratories (Shropshire, UK) Model 210 and Model 220). Additional detectors may include an IR4 infrared detector from PolymerChAR (Valencia, Spain), Precision Detectors (Amherst, Mass.), a dual angle laser light scattering detector Model 2040, and a Viscotek (Houston, Tex.) 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 generally refers to a conventional GPC. Depending on the sample, either a 15 degree angle or a 90 degree angle of the light scattering detector is used for calculation purposes.

[0199] Data collection was performed using Viscotek TriSEC software version 3 and 4-channel Viscotek data manager DM400. The system is equipped with an online solvent degasser from Polymer Labs (Shropshire, UK). Suitable high temperature GPC columns can be used, such as four 30cm long Shodex HT803 13 micron columns or four 30cm Polymer Labs columns (MixA LS, Polymer Labs) of 20 micron mixed pore size fillers. The sample turntable chamber is operated at 140°C, and the column chamber is operated at 150°C. The sample is prepared with a concentration of 0.1 gram of polymer in 50 milliliters of solvent. Chromatographic solvent and sample preparation solvent contain 200ppm butylated hydroxytoluene (BHT). Both solvents are sprayed with nitrogen. The polyethylene sample is gently stirred for four hours (4 hours) at 160°C. The injection volume is 200 microliters (μL). The flow rate through GPC is set to 1 ml / min.

[0200] NMR 13 C and 1 H) :

[0201] NMR analyses were performed using standard NMR solvents such as chloroform or benzene, at room temperature, and data were acquired on a Varian 500 MHz spectrometer.

[0202] Diffusion NMR: The experiment used 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 using pulsed field gradient NMR by diffusion detected by 1H and 13C, where the echo of the dual stimulation mitigated any artifacts by thermal convection. In general, this method utilizes the spatial variation of the magnetic field (i.e., the magnetic field gradient (g)) to physically mark the spatial position of molecular ensembles during well-defined time intervals, thereby coupling the NMR peak intensity to the self-diffusion (D) of each molecule. D is quantified 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 nucleus, g is the gradient strength, δ is the gradient pulse duration and Δ is the diffusion time. Considering that peaks from the same molecule must produce the same D, such methods are able to achieve intrinsic separation of NMR peaks by the D associated with each peak without interfering with spectral resolution. This method can also be considered as an analogue of size exclusion chromatography (SEC) in nature, i.e. large molecules diffuse slower / elute earlier, or vice versa. Therefore, the measurement provides unambiguous intermolecular information to be compared with D 端 With D 主链 To show whether the polymer backbone is terminated by a specific end group.

[0203]

[0204] GCMS :

[0205] Tandem gas chromatography / low resolution mass spectrometry using electron impact ionization (EI) was performed at 70 eV on an Agilent Technologies 6890N series gas chromatograph equipped with an Agilent Technologies 5975 Inert XL mass selective detector and an Agilent Technologies capillary column (HP1MS, 15 m x 0.25 mm, 0.25 micron) for the following:

[0206] Programmatic approach :

[0207] Oven equilibration time of 0.5 min at 50 °C

[0208] Then 25℃ / min to 200℃ and keep for 5min

[0209] Running time: 11 minutes

[0210] Example

[0211] The following examples are intended to illustrate some embodiments of the invention and should not be construed as limiting the scope of the invention described in the claims.

[0212] Unless otherwise stated, all materials and reagents are commercially available, for example from Sigma Aldrich.

[0213] Example 1

[0214]

[0215] The reaction of Example 1 was carried out in an inert nitrogen atmosphere glove box according to the above exemplary and non-limiting reaction scheme. 5.88 mL of 0.30 M dioctyl zinc was dissolved in Isopar TM The solution in E (1.76mmol) was added to a 20mL vial. The solution was heated to 60°C. 0.500g of methyl 2-(chloromethyl)acrylate (3.72mmol, 2 equivalents) was added dropwise to the hot dioctylzinc solution. During the slow addition, the solution changed from light brown to transparent and became turbid with a visible white precipitate. After several minutes, the precipitate settled as a sticky yellow residue on the bottom of the vial. After 48 hours at 60°C, 83mg of hexamethylenebenzene (0.511mmol) was added as an NMR internal standard. The NMR conversion was calculated to be 62.6%. The NMR analysis is shown in Figure 1A and Figure 1B In. Figure 1C and Figure 1D As can be seen, GC-MS of the reaction aliquot 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 2% ethyl acetate / hexane mixture to remove Zn salts and internal standard. 405 mg of product was isolated (51%).

[0216] Example 2

[0217]

[0218] The reaction was carried out in a nitrogen atmosphere glove box. Before the reaction started, tert-butyl acrylate was passed through an alumina cartridge to remove inhibitors. Tert-butyl acrylate (4 mL, 27.6 mmol), 0.2 M AIBN in toluene (0.140 mL, 0.028 mmol, 0.001 equiv.), and 4-cyano-4-(((dodecylthio)carbonylthio)thio)pentanoic acid (0.113 g, 0.280 mmol, 0.01 equiv.) were added to a 20 mL vial with a stirring bar. The reaction mixture was heated to 60 ° C and stirred for 1 h. 1H NMR monitoring. After 3 hours, the reaction mixture became a very viscous yellow liquid. The reaction was terminated by removing from the glove box and exposing the vial to air. The viscous liquid was dissolved in 15 mL of THF to redissolve the polymer. The polymer was precipitated by the following steps: the THF solution was added to about 300 mL of cold hexane in a dry ice / acetone bath, the liquid was quickly decanted, and the yellow solid was collected at the bottom of the jar while still immersed in the dry ice bath. The polymer was washed with chlorobenzene to remove excess hexane and dried overnight on a Schlenk tube.

[0219] Subsequently, the polymer was returned to the glove box and dissolved in about 3 mL of toluene. The polymer was degassed by stirring the toluene solution with the cap of the vial for 10 minutes. After adding the compound prepared in Example 1 and heating at 60°C for a weekend, NMR showed that the reaction did not proceed significantly. An additional 59 μL of 0.2M AIBN was added and heating was continued at 60°C. NMR again showed no reaction. An additional 2 mL of toluene was added to the reaction mixture to reduce the viscosity. 59 μL of 0.2M AIBN was added and the reaction was heated to 60°C. After 48 hours, the reaction appeared to have occurred due to the decrease in the relative intensity of the methine signal.

[0220] The polymer was precipitated by addition to cold hexane cooled in a dry ice / acetone bath. The polymer was a yellow solid that turned back into a viscous gooey liquid once the hexane was slightly heated outside the dry ice bath. The solvent was removed on a rotary evaporator and Schlenk tube (50°C). The NMR and diffuse NMR spectra of Example 2 were obtained at Figure 2A and Figure 2B Table 1 below provides some data before and after the reaction of Example 2:

[0221] Table 1.

[0222]

Claims

1. A method for preparing an olefin-acrylate block copolymer, the method comprising: a) performing reversible addition-fragmentation chain transfer (RAFT) polymerization by combining a RAFT material comprising an acrylate monomer, a free radical initiator, and a RAFT agent, thereby forming a macroinitiator; and b) combining reactive materials including an alpha-substituted acrylate, a free radical initiator, and the macroinitiator, thereby forming the olefin-acrylate block copolymer, wherein: The α-substituted acrylate has formula (II): The acrylate monomer has formula (III): The RAFT agent has formula (IV): The macroinitiator has formula (V): The olefin-acrylate block copolymer has formula (VI): And among them: Each R1 is independently hydrogen or a C1-C30 hydrocarbon group; Each R2 is independently hydrogen or a methyl group; Each R is independently a C1-C26 hydrocarbon group or a polyolefin group; R11 is selected from the group consisting of: optionally substituted alkyl; optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic ring; optionally substituted alkylthio; optionally substituted alkoxy; and optionally substituted dialkylamino; and wherein R11 is a free radical leaving group capable of initiating free radical polymerization; each Z is selected from the group consisting of hydrogen, chlorine, optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl, carboxyl (-COOH), optionally substituted acyloxy (-O2CR"), optionally substituted carbamoyl (-CONR"2), cyano (-CN), dialkyl or diaryl-phosphono, and dialkyl or diaryl-phosphinyl; Each R" is independently selected from the group consisting of: optionally substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclic, aralkyl, alkaryl, wherein the substituents are independently selected from the group consisting of: epoxy, hydroxy, alkoxyacyl, acyloxy, carboxyl, sulfonic acid, alkoxy or aryloxycarbonyl, isocyanato, cyano, silyl, halo and dialkylamino; and Each I· is independently a free radical initiator or a free radical leaving group derived from R11 of a RAFT agent that initiates free radical polymerization; each n is 2 to 500, and m is 1 to 50.

2. The method according to claim 1, wherein each R is independently a C1-C26 hydrocarbon group.

3. The method of claim 1, wherein each R is independently a polyolefin-based group. The method according to claim 3 , wherein the polyolefin group is a vinyl polymer group. The method according to claim 3 , wherein the polyolefin-based group is a propylene-based polymer-based group.

6. The method according to any one of claims 3 to 5, wherein the polyolefin-based group can be defined by the nature of RH, and wherein the number average molecular weight of RH is greater than 365 g / mol.

7. The method according to any one of claims 1 to 5, wherein each of steps a) and b) is performed at a temperature of 40°C to 150°C.

8. The method of claim 1, wherein the optionally substituted aryloxycarbonyl is -COOR", each R" in the -COOR" being independently selected from an aryl group and an alkaryl group.

9. The method according to claim 1, wherein the dialkyl or diaryl-phosphonic acid group is P(=O)OR"2, and the dialkyl or diaryl-phosphinate group is -P(=O)R"2, the - Each R" in P(=O)OR"2 and -P(=O)R"2 is independently selected from the group consisting of optionally substituted C1-C18 alkyl, aryl, aralkyl and alkaryl, wherein the substituents are independently selected from the group consisting of epoxy, hydroxy, alkoxyacyl, acyloxy, carboxyl, sulfonic acid, alkoxy or aryloxycarbonyl, isocyanate, cyano, silyl, halide and dialkylamino.

10. The olefin-acrylate block copolymer prepared by the method according to any one of claims 1 to 9.

11. An olefin-acrylate block copolymer having formula (VI): And among them: Each R1 is independently hydrogen or a C1-C30 hydrocarbon group; R2 is hydrogen or a methyl group; R is a C1-C26 hydrocarbon group or a polyolefin group; R11 is selected from the group consisting of: optionally substituted alkyl; optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic ring; optionally substituted alkylthio; optionally substituted alkoxy; and optionally substituted dialkylamino; and wherein R11 is a free radical leaving group capable of initiating free radical polymerization; Z is selected from the group consisting of hydrogen, chlorine, optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl, carboxyl (-COOH), optionally substituted acyloxy (-O2CR"), optionally substituted carbamoyl (-CONR"2), cyano (-CN), dialkyl or diaryl-phosphono and dialkyl or diaryl-phosphinyl; Each R" is independently selected from the group consisting of: optionally substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclic, aralkyl, alkaryl, wherein the substituents are independently selected from the group consisting of: epoxy, hydroxy, alkoxyacyl, acyloxy, carboxyl, sulfonic acid, alkoxy or aryloxycarbonyl, isocyanato, cyano, silyl, halide and dialkylamino; I is a free radical initiator or a free radical leaving group obtained from R11 of a RAFT agent that initiates free radical polymerization; n is 2 to 500, and m is 1 to 50.

12. The olefin-acrylate block copolymer according to claim 11, wherein the optionally substituted aryloxycarbonyl group is -COOR", and each R" in the -COOR" is independently selected from an aryl group and an alkylaryl group.

13. The olefin-acrylate block copolymer according to claim 11, wherein the dialkyl or diaryl-phosphonic acid group is -P(=O)OR"2, and the dialkyl or diaryl-phosphinous acid group is -P(=O)R"2, each R" in the -P(=O)OR"2 and -P(=O)R"2 is independently selected from the group consisting of optionally substituted C1-C18 alkyl, aryl, aralkyl and alkaryl, wherein the substituent is independently selected from the group consisting of epoxy, hydroxyl, alkoxyacyl, acyloxy, carboxyl, sulfonic acid, alkoxy or aryloxycarbonyl, isocyanato, cyano, silyl, halide and dialkylamino.

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