Multi-block copolymer and method for preparing the same

Abstract

This invention relates to multiblock copolymers and their preparation methods. Because the chain structure of the multiblock copolymer is nearly symmetrical, it can provide resin compositions with excellent compatibility and high impact strength.

Description

Technical Field

[0001] This invention relates to multiblock copolymers and their preparation methods, and more specifically, to polyolefin-polystyrene multiblock copolymers comprising polystyrene blocks and polyolefin blocks, and to a method for manufacturing the multiblock copolymer.

[0002] Cross-referencing of related applications

[0003] This application claims the benefit of Korean Patent Application No. 10-2021-0130753, filed on October 1, 2021, the full text of which is incorporated herein by reference. Prior Technology

[0004] Block copolymers are widely used not only in plastics for everyday applications but also in high-tech devices, and their research and development are actively pursued. In particular, styrene-olefin copolymer resins, which include both polyolefin (POs) and polystyrene (PSs) blocks, possess excellent properties such as heat resistance, light resistance, and elasticity, and are therefore useful in various technical fields.

[0005] Polyolefin-polystyrene block copolymers, such as styrene-ethylene-butene-styrene (SEBS) or styrene-ethylene-propylene-styrene (SEPS), currently have a global market of hundreds of thousands of tons. A representative example of a styrene-olefin copolymer resin is the polystyrene-block-poly(ethylene-co-1-butene)-block-polystyrene (SEBS) triblock copolymer. This SEBS triblock copolymer exhibits thermoplastic elastomer properties due to the separation of the rigid polystyrene blocks from the soft poly(ethylene-co-1-butene) matrix in its structure, which act as physical crosslinking points. Because of these properties, SEBS is more widely used in a range of products requiring rubber and plastics, and the demand for SEBS is increasing significantly as its applications expand.

[0006] [Previous Technical Documents]

[0007] [Patent Literature]

[0008] (Patent Document 1) Korean Patent Publication No. 10-1657925 Summary of the Invention

[0009] The technical problem to be solved

[0010] The present invention provides a multiblock copolymer comprising polystyrene-based blocks and polyolefin-based blocks, and more particularly, provides the multiblock copolymer and its preparation method, wherein the multiblock copolymer, due to its nearly symmetrical chain structure, can provide a resin composition with excellent compatibility and high impact strength. Technical means to solve the problem

[0011] According to one aspect of the present invention, a multiblock copolymer and a method for preparing the multiblock copolymer are provided.

[0012] (1) The present invention proposes a multiblock copolymer comprising polystyrene blocks including repeating units derived from aromatic vinyl monomers, and polyolefin blocks including repeating units derived from ethylene and repeating units derived from α-olefin monomers, wherein when the storage modulus G' and the loss modulus G” measured by dynamic mechanical analysis are plotted as the y-axis and x-axis respectively, the multiblock copolymer satisfies condition a): a slope of 2.00 to 4.00 at 130°C, and condition b): a slope of 3.00 to 5.00 at 190°C.

[0013] (2) In (1) above, the present invention proposes a multi-block copolymer, wherein the α-olefin is selected from one or more of the following groups: 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, and 3,4-dimethyl-1-hexene.

[0014] (3) In (1) or (2) above, the present invention proposes a multiblock copolymer, wherein the slope of the multiblock copolymer at 130°C is lower than the slope at 190°C.

[0015] (4) In (1) to (3) above, the present invention proposes a multiblock copolymer, wherein the multiblock copolymer further meets condition c): the difference between the slope at 130°C and the slope at 190°C is 0.50 to 2.00.

[0016] (5) In (1) to (4) above, the present invention proposes a multiblock copolymer, wherein the multiblock copolymer further conforms to the slope of 2.00 to 5.00 in the range of 130°C to 250°C.

[0017] (6) In (1) to (5) above, the present invention provides a multiblock copolymer, wherein the multiblock copolymer further meets the condition of a slope of 3.00 to 4.80 at 250°C.

[0018] (7) In any of (1) to (6) above, the present invention provides a multiblock copolymer, wherein the molecular weight distribution of the multiblock copolymer is 1.5 to 3.0 as measured by gel permeation chromatography (GPC).

[0019] (8) The present invention provides a method for preparing a multiblock copolymer of any one of (1) to (5) above, the method comprising: (S1) using an organozinc compound as a chain transfer agent, reacting ethylene with an α-olefin monomer in the presence of a catalyst composition including a transition metal compound to prepare a polyolefin block copolymer; and (S2) reacting an aromatic vinyl monomer with the polyolefin block in the presence of an anionic polymerization initiator to prepare a multiblock copolymer.

[0020] (9) In (8) above, the present invention provides a method for preparing a multiblock copolymer, wherein the transition metal compound is a compound represented by the following formula 1.

[0021] [Formula 1]

[0022] In Equation 1 above,

[0023] M is Ti, Zr, or Hf.

[0024] R1 to R4 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, or a substituted or unsubstituted C6 to C20 aryl, and two or more adjacent ones may be linked together to form a ring.

[0025] R5 and R6 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group, wherein the substitution is a C1 to C12 alkyl group.

[0026] R7 is independently a substituted or unsubstituted C4 to C20 alkyl, a substituted or unsubstituted C4 to C20 cycloalkyl, or a substituted or unsubstituted C6 to C20 aryl.

[0027] n is 1 to 5, and

[0028] Y1 and Y2 are each independently a halogen, substituted or unsubstituted C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, C7 to C20 aralkyl, C5 to C20 heteroaryl, C1 to C20 alkoxy, substituted or unsubstituted C5 to C20 aryloxy, C1 to C20 alkylamino, C5 to C20 arylamino, C1 to C20 alkylthio, C5 to C20 arylthio, C1 to C20 alkylsilyl, C5 to C20 arylsilyl, hydroxyl, amino, thio, silyl, cyano, or nitro.

[0029] (10) In (8) or (9) above, the present invention provides a method for preparing a multiblock copolymer, wherein the organozinc compound is represented by the following formula 5.

[0030] [Formula 5]

[0031] In Equation 5 above,

[0032] R8 and R10 are each independently a single bond or a C1 to C10 alkyl group, R9 is a C1 to C10 alkyl group or -SiR11R12-, and R11 and R12 are each independently a C1 to C10 alkyl group.

[0033] (11) In any of (8) to (10) above, the present invention provides a method for preparing a multiblock copolymer, wherein the organozinc compound is prepared by reacting a Grignard reagent containing a styrene group with an alkyl zinc alkoxide.

[0034] (12) In any of (8) to (11) above, the present invention provides a method for preparing a multiblock copolymer, wherein the Grinner reagent containing styrene atoms is represented by the following formula 7.

[0035] [Formula 7]

[0036] In Equation 7 above,

[0037] R8 and R10 are each independently a single bond or a C1 to C10 alkyl group, R9 is a C1 to C10 alkyl group or -SiR11R12-, R11 and R12 are each independently a C1 to C10 alkyl group, and X is a halogroup.

[0038] (13) In any of (8) to (12) above, the present invention provides a method for preparing a multiblock copolymer, wherein the anionic polymerization initiator comprises an alkyl lithium compound containing an allyl group, wherein the allyl group is combined with lithium.

[0039] (14) In any of (8) to (13) above, the present invention provides a method for preparing a multiblock copolymer, wherein the alkyl lithium compound is represented by the following formula 11.

[0040] [Equation 11]

[0041] In Equation 11 above,

[0042] R 13 is hydrogen or a C1 to C20 hydrocarbon, and

[0043] Am refers to amine compounds represented by the following formula 12.

[0044] [Equation 12]

[0045] In Equation 12 above,

[0046] R14 to R18 are each independently hydrogen or C1 to C20 hydrocarbons, and

[0047] a and b are each independent integers from 0 to 3, where a and b are not both 0 at the same time. The benefits of invention

[0048] The multiblock copolymer proposed in this invention exhibits excellent compatibility due to its nearly symmetrical chain structure, and because the composition made by including the multiblock copolymer exhibits excellent impact strength, it can be used to manufacture multiblock copolymer compositions. Simple Explanation of the Diagram

[0049] [Figure 1] is the G'-G” plot of Example 2. It is obtained by measuring the storage modulus G' and the loss modulus G” based on temperature using dynamic mechanical analysis method, and then plotting the obtained values ​​as the y-axis and x-axis respectively.

[0050] [Figure 2] is a graph showing the slope values ​​of the storage modulus at various temperatures in the examples and comparative examples.

[0051] [Figure 3] is a graph with the elongation in each example and comparative example as the x-axis and the tensile strength in each example and comparative example as the y-axis. Implementation

[0052] The invention will now be described in more detail to aid in understanding it.

[0053] It will be understood that the words and terms used in the description of this invention and the claims should not be limited to their meanings as defined in a commonly used dictionary. It will be further understood that such words and terms should be interpreted based on the inventor's ability to appropriately define them to best explain the invention, in a meaning consistent with the context of the related art and the technical concept of the invention.

[0054] In this specification, the term "alkyl" refers to a straight-chain or branched hydrocarbon group.

[0055] In this invention, the term "alkyl" refers to a straight-chain or branched hydrocarbon group.

[0056] In this invention, the term "alkenyl" refers to a straight-chain or branched alkenyl group.

[0057] In this invention, the "aryl" preferably has 6 to 20 carbon atoms, and may specifically be phenyl, naphthyl, anthraceneyl, pyridyl, dimethylaniline, anisoleyl, etc., but is not limited thereto.

[0058] In this invention, "alkylaryl" refers to an aryl group substituted with the aforementioned alkyl group.

[0059] In this invention, "aryl group" refers to an alkyl group substituted with the above-mentioned aryl group.

[0060] In this specification, the term "alkylsilyl" may refer to a silyl group substituted with an alkyl group having 1 to 20 carbon atoms, such as trimethylsilyl or triethylsilyl.

[0061] In this invention, "alkylamino" refers to an amino group substituted with the above-mentioned alkyl group, such as dimethylamino, diethylamino, etc., but is not limited thereto.

[0062] In this invention, unless otherwise stated, "hydrocarbon group" refers to a monovalent hydrocarbon group having 1 to 20 carbon atoms and consisting only of carbon and hydrogen, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl, or aralkyl, regardless of its structure.

[0063] In this specification, the term "composition" includes not only reaction products and decomposition products formed from the materials of the corresponding composition, but also mixtures of materials containing the corresponding composition.

[0064] In this specification, the term "polymer" refers to a polymer compound obtained by polymerizing monomers (whether of the same or different kinds). Therefore, the general term "polymer" encompasses the terms "homopolymer" (usually referring to a polymer obtained from only one monomer) and "interpolymer" as defined below.

[0065] In this specification, the term "copolymer" refers to a polymer obtained by polymerizing at least two different monomers.

[0066] In this instruction manual, the digit 0 after the decimal point "." can be omitted.

[0067] The present invention will be described in detail below.

[0068] [Multiblock copolymer]

[0069] The multiblock copolymer of the present invention comprises polystyrene blocks including repeating units derived from aromatic vinyl monomers, and polyolefin blocks including repeating units derived from ethylene and repeating units derived from α-olefin monomers, wherein the multiblock copolymer meets the following conditions when plotted with temperature storage modulus G' and temperature loss modulus G” as the y-axis and x-axis, respectively, by means of dynamic mechanical analysis.

[0070] a) The slope at 130℃ is 2.00 to 4.00, and

[0071] b) The slope at 190°C is 3.00 to 5.00.

[0072] The multiblock copolymer of this invention is prepared using a specific transition metal compound with a novel structure, as described below, as a catalyst. This multiblock copolymer has a high weight-average molecular weight, which is an important factor determining the physical properties of the copolymer, and its chain structure is nearly symmetrical. The multiblock copolymer of this invention comprises polystyrene blocks with repeating units derived from aromatic vinyl monomers, and polyolefin blocks comprising repeating units derived from ethylene and repeating units derived from α-olefin monomers. Because the chain structure of this multiblock copolymer is nearly symmetrical, it has a uniform polystyrene (PS) block size. Accordingly, when a resin composition is prepared by blending this multiblock copolymer with a polyolefin (e.g., polypropylene), the polyolefin blocks are uniformly distributed, thus the multiblock copolymer of this invention exhibits excellent compatibility with polyolefins (e.g., polypropylene). Furthermore, due to the uniform physical crosslinking of the polystyrene block blocks, the multiblock copolymer of this invention also exhibits excellent physical properties.

[0073] The multiblock copolymer of the present invention is characterized in that the G'-G” diagram meets the following conditions, wherein the G'-G” diagram is plotted by using the temperature-dependent storage modulus G' and temperature-dependent loss modulus G” measured by dynamic mechanical analysis as the y-axis and x-axis, respectively.

[0074] In one example of the present invention, the G'-G” graph conforms to a) a slope of 2.00 to 4.00 at 130°C, and b) a slope of 3.00 to 5.00 at 190°C, and a slope in the range of 2.00 to 5.00 in the range of 130°C to 250°C.

[0075] In one example of the invention, a) the slope of the G'-G” graph at 130°C may specifically be 2.20 or higher, 2.40 or higher, 2.50 or higher, 3.80 or lower, 3.60 or lower, or 3.40 or lower, and more specifically, may be 2.60 to 3.30.

[0076] Furthermore, in one example of the present invention, b) the slope of the G'-G” graph at 190°C may specifically be 3.00 or higher, 3.05 or higher, 3.10 or higher, 3.12 or higher, 4.80 or lower, 4.70 or lower, or 4.60 or lower, and more specifically, may be 3.12 to 4.50.

[0077] Furthermore, in one example of the present invention, the G'-G” graph may specifically meet the condition that the slope is in the range of 2.20 or higher, 2.40 or higher, 2.50 or higher, 4.80 or lower, 4.70 or lower, or 4.60 or lower within the range of 130°C to 250°C, and more specifically 2.60 to 4.50.

[0078] The slope of the multiblock copolymer at 130°C may be lower than that at 190°C, and the multiblock copolymer may further satisfy condition c): the difference between the slope at 130°C and the slope at 190°C is 0.50 to 2.00. In one example of the invention, condition c) the difference between the slope at 130°C and the slope at 190°C may be 0.50 or higher, 0.52 or higher, 0.55 or higher, 0.57 or higher, 1.90 or lower, 1.80 or lower, or 1.70 or lower, and more specifically, may be 0.55 to 1.65.

[0079] Furthermore, in one example of the present invention, b) the slope of the G'-G” graph at 250°C may be 3.00 to 4.80, specifically, 3.00 or higher, 3.05 or higher, 3.10 or higher, 3.13 or higher, or 3.15 to 4.80, 4.70 or lower, 4.60 or lower, 4.5 or lower, or 4.40 or lower, and more specifically, may be 3.15 to 4.50.

[0080] When the temperature-dependent storage modulus G' and temperature-dependent loss modulus G” of a multiblock copolymer are measured using dynamic mechanical analysis, and a G'-G” diagram is plotted with the storage modulus G' and loss modulus G” as the y-axis and x-axis, respectively, the order-disorder temperature (T ODT) can be obtained using this G'-G” diagram. At temperatures equal to or below the order-disorder temperature (T ODT), the copolymer exhibits an ordered state, while at temperatures equal to or above the order-disorder temperature (T ODT), the copolymer exhibits a disordered state. Furthermore, at temperatures equal to or below the order-disorder temperature (T ODT), the microblocks of the copolymer change with temperature, causing the slope of the G'-G” diagram to change. On the other hand, at temperatures equal to or above the order-disorder temperature (T ODT), the slope of the G'-G” diagram does not change, even when the temperature is changed.

[0081] The multiblock copolymer of the present invention is characterized in that the slopes of the G'-G' diagram at 130°C (a) and at 190°C (b) of the G'-G' diagram with the above properties conform to the above range, and the multiblock copolymer of the present invention conforming to the above range can exhibit improved physical properties, such as excellent elongation and tensile strength and an appropriate degree of 300% modulus.

[0082] The weight average molecular weight (MW) of the multiblock copolymer is from 100,000 to 300,000 g / mol, and specifically, it can be 105,000 g / mol or higher, 300,000 g / mol or lower, or 250,000 g / mol or lower, and more specifically, it can be from 120,000 to 200,000 g / mol.

[0083] The molecular weight distribution (PDI) of the multiblock copolymer is from 1.5 to 3.0, and specifically, it may be 1.55 or higher, 1.6 or higher, 1.65 to 2.8, 2.6 or lower, 2.5 or lower, 2.3 or lower, or 2.0 or lower, and more specifically, it may be from 1.65 to 2.0.

[0084] The molecular weight distribution is calculated by the ratio of (weight average molecular weight) to (number average molecular weight), and the weight average molecular weight and number average molecular weight are the molecular weights of polystyrene converted by gel permeation chromatography (GPC).

[0085] In addition to meeting the slope condition of the G'-G" diagram, the multiblock copolymer of the present invention can also meet the molecular weight distribution (PDI).

[0086] The multiblock copolymers of the present invention must include branches (wherein the polyolefin blocks of the multiblock copolymer are derived from the self-chain), but the branches included are fewer than those of typical polyolefin-polystyrene block copolymers (specifically, styrene-ethylene-butene-styrene copolymers (SEBS) and styrene-ethylene-propylene-styrene copolymers (SEPS) obtained by a two-step process of typical anionic polymerization and hydrogenation), while exhibiting excellent physical properties.

[0087] The multiblock copolymer of the present invention is a polyolefin-polystyrene multiblock copolymer, which comprises polystyrene blocks including repeating units derived from aromatic vinyl monomers, and polyolefin blocks including repeating units derived from ethylene and repeating units derived from α-olefin monomers, wherein the α-olefin monomers may be C5 to C20 α-olefins, specifically C5 to C14 α-olefins.

[0088] In one example of the invention, the α-olefin may be selected from one or more of the group consisting of: 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, and 3,4-dimethyl-1-hexene, and more specifically, may be 1-hexene.

[0089] Measured by 1H NMR (500 MHz, tetrachloroethane-d2, standard TMS) spectroscopy, the content of repeating units derived from α-olefin monomers in the multiblock copolymer of the present invention can be 20 mol% to 40 mol%, and specifically, the content of repeating units derived from α-olefin monomers can be 24 wt% or higher, 25 wt% or higher, 25.5 wt% or higher, 26 wt% or higher, 27 wt% or higher, 28 wt% to 39 wt%, 38 wt% or lower, 37 wt% or lower, 36 wt% or lower, 35 wt% or lower, 34 wt% or lower, or 32.2 wt% or lower, and more specifically, can be 28 wt% to 34 wt%.

[0090] When the content of the repeating unit derived from the α-olefin monomer is within the above-mentioned weight % range, the multiblock copolymer can further exhibit excellent elongation and tensile strength.

[0091] In one example of the present invention, the aromatic vinyl monomer may be a C6 to C20 aromatic vinyl monomer. For example, the aromatic vinyl monomer may be an aromatic vinyl monomer including ethylene substituted with C6 to C20 aryl groups, ethylene substituted with phenyl groups, etc., specifically phenethyl, α-methylstyrene, vinyltoluene, alkylstyrene substituted with C1-3 alkyl groups (e.g., o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, etc.) or halogen-substituted styrene, and more specifically styrene.

[0092] Measured by 1H NMR (500 MHz, tetrachloroethane-d2, standard TMS) spectroscopy, the content of repeating units derived from aromatic vinyl monomers in the multiblock copolymer of the present invention can be from 15 mol% to 35 mol%, and specifically, the content of repeating units derived from aromatic vinyl monomers can be 17 wt% or higher, 19 wt% or higher, 20 wt% or higher, 21 wt% or higher, 22 wt% or higher, 23 wt% or higher, 24 wt% to 33 wt%, 31 wt% or lower, 30 wt%, 29 wt% or lower, 28 wt% or lower, or 27 wt% or lower, and more specifically, can be from 20 wt% to 27 wt%.

[0093] Furthermore, the multiblock copolymer of the present invention may more specifically be a polystyrene-poly(ethylene-co-1-hexene)-polystyrene block copolymer.

[0094] [Preparation of Multiblock Copolymers]

[0095] The method for preparing the multiblock copolymer of the present invention includes (S1) using an organozinc compound as a chain transfer agent, reacting ethylene with α-olefin monomers in the presence of a catalyst composition including a transition metal compound to prepare a polyolefin block copolymer; and (S2) reacting aromatic vinyl monomers with polyolefin blocks in the presence of an alkyllithium compound and an amine compound to prepare a multiblock copolymer.

[0096] Step (S1)

[0097] Step (S1) is a step of preparing polyolefin blocks by reacting ethylene with α-olefin monomers in the presence of a catalyst composition including transition metal compounds, using organozinc as a chain transfer agent.

[0098] According to embodiments of the present invention, the transition metal compound is a catalyst used to grow olefin polymers via coordination chain transfer polymerization, and may be a catalyst composition comprising a primary catalyst (which is a transition metal) and an auxiliary catalyst.

[0099] In this invention, the transition metal compound is a compound represented by Formula 1 below.

[0100] [Formula 1]

[0101] In Equation 1 above,

[0102] M is Ti, Zr, or Hf.

[0103] R1 to R4 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, or a substituted or unsubstituted C6 to C20 aryl, and two or more adjacent ones may be linked together to form a ring.

[0104] R5 and R6 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group, wherein the substitution is a C1 to C12 alkyl group.

[0105] R7 is independently a substituted or unsubstituted C4 to C20 alkyl, a substituted or unsubstituted C4 to C20 cycloalkyl, or a substituted or unsubstituted C6 to C20 aryl.

[0106] n is 1 to 5, and

[0107] Y1 and Y2 are each independently a halogen, substituted or unsubstituted C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, C7 to C20 aralkyl, C5 to C20 heteroaryl, C1 to C20 alkoxy, substituted or unsubstituted C5 to C20 aryloxy, C1 to C20 alkylamino, C5 to C20 arylamino, C1 to C20 alkylthio, C5 to C20 arylthio, C1 to C20 alkylsilyl, C5 to C20 arylsilyl, hydroxyl, amino, thio, silyl, cyano, or nitro.

[0108] Specifically, in Equation 1 above, M can be Hf.

[0109] Furthermore, specifically, in Formula 1 above, R1 to R4 can each be independently hydrogen, or substituted or unsubstituted C1 to C20 alkyl groups, wherein two or more adjacent ones can be linked together to form a ring. Alternatively, R1 to R2 can each be independently C1 to C20 alkyl groups, which are linked together to form a C5 to C20 aromatic ring, and R3 and R4 can be hydrogen.

[0110] Furthermore, specifically, in Formula 1 above, R5 and R6 can each be hydrogen, or substituted or unsubstituted C6 to C20 aryl groups, wherein the substitution can be C1 to C6 alkyl substitution.

[0111] Furthermore, specifically, in Formula 1 above, R7 can be independently a substituted or unsubstituted C4 to C20 alkyl, a substituted or unsubstituted C4 to C20 cycloalkyl, or a substituted or unsubstituted C6 to C20 aryl.

[0112] Specifically, in Equation 1 above, n can be 1 to 3, with 2 being the most preferred.

[0113] Specifically, in Formula 1 above, Y1 and Y2 can each be independently C1 to C20 alkyl groups.

[0114] More specifically, the transition metal compound represented by Formula 1 above can be a compound represented by Formula 1a below.

[0115] [Equation 1a]

[0116] In the above formula 1a,

[0117] M, R5 to R7, and Y1 and Y2 are defined as above.

[0118] The transition metal compound represented by Formula 1 above may be specifically selected from the following compounds, but is not limited thereto. All transition metal compounds corresponding to Formula 1 are included in this invention.

[0119] [Equation 1-1]

[0120] [Equation 1-2]

[0121] [Equation 1-3]

[0122] [Equations 1-4]

[0123] [Equations 1-5]

[0124] [Equations 1-6]

[0125] [Equations 1-7]

[0126] [Equations 1-8]

[0127] Furthermore, the present invention provides a coordination compound represented by Formula 2 below.

[0128] [Equation 2]

[0129] In Equation 2 above,

[0130] R1 to R4 are each independently a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, or a substituted or unsubstituted C6 to C20 aryl, and two or more adjacent ones may be linked together to form a ring.

[0131] R5 and R6 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group, wherein the substitution is a C1 to C12 alkyl group.

[0132] R 7 is independently a substituted or unsubstituted C4 to C20 alkyl, a substituted or unsubstituted C4 to C20 cycloalkyl, or a substituted or unsubstituted C6 to C20 aryl, and

[0133] n is 1 to 5.

[0134] That is, the transition metal compound of the present invention can be prepared by a step including reacting the ligand compound represented by Formula 2 below with the compound represented by Formula 3 below.

[0135] [Equation 2]

[0136] [Formula 3]

[0137] In the above formula,

[0138] R1 to R7, M, and Y1 and Y2 are defined the same as above.

[0139] Meanwhile, when preparing the transition metal compound represented by Formula 1 of the present invention, the reaction can be carried out by the following procedure.

[0140] [Reaction Formula 1]

[0141] [Reaction 2]

[0142] In this invention, the organozinc compound is used as a chain transfer agent to induce chain transfer during the polymerization reaction of copolymers. The chain transfer agent can be a chain transfer agent for preparing block copolymers by coordination chain transfer polymerization.

[0143] The auxiliary catalyst may be a compound represented by Formula 4 below, and the compound represented by Formula 4 below may be used as an auxiliary catalyst, a cleaning agent, or both.

[0144] [Formula 4]

[0145] In Equation 4 above,

[0146] Ra is independently a halogenated group, a C1 to C20 hydrocarbon group, or a C1 to C20 hydrocarbon group substituted with a halogen, and

[0147] m is an integer of 2 or greater.

[0148] There are no particular limitations on the compounds represented by Formula 4 above, as long as they are alkylaluminoxanes. Preferred examples include modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., and particularly preferred compounds are modified methylaluminoxane (MMAO).

[0149] The compound represented by Formula 4 above is an oligomer formed by the reaction of alkylaluminum and water. When this compound is used as an auxiliary catalyst, chain transfer is reduced. Therefore, high molecular weight copolymers can be obtained, and the side reaction of forming homopolymers is also prevented. Thus, finally, polyolefin-polystyrene multiblock copolymers exhibiting excellent physical properties (e.g., high tensile strength) can be obtained.

[0150] Meanwhile, while the compound represented by Formula 4 inhibits the aforementioned chain transfer, if, for example, an alkylaluminum compound is used as an auxiliary catalyst, many chain transfers will occur, resulting in a decrease in the molecular weight of the copolymer and an increase in the formation of homopolymer olefins, which will lead to the deterioration of the physical properties of the block copolymer.

[0151] In one example of the present invention, the chain transfer agent may include an organozinc compound represented by Formula 5 below, and more specifically, the chain transfer agent may include 96 mol% or more of the organozinc compound represented by Formula 5 below, and preferably, the chain transfer agent does not contain any by-reaction products other than the organozinc compound represented by Formula 5 below.

[0152] [Formula 5]

[0153] In Equation 5 above,

[0154] R8 and R10 may each be a single bond or a C1 to C10 alkyl group, R9 may be a C1 to C10 alkyl group or -SiR11R12-, and R11 and R12 may each be a C1 to C10 alkyl group.

[0155] Furthermore, according to embodiments of the present invention, in Formula 5 above, R8 and R10 may each be independently a single bond or a C1 to C10 alkyl group, R9 may be a C1 to C10 alkyl group or -SiR11R12-, and R11 and R12 may each be independently a C1 to C10 alkyl group.

[0156] According to embodiments of the present invention, the organozinc compound represented by Formula 5 may be one of the group consisting of organozinc compounds represented by Formulas 5-1 to 5-4, and preferably any one of Formulas 5-3 and 5-4.

[0157] [Equation 5-1]

[0158] [Equation 5-2]

[0159] [Equation 5-3]

[0160] [Equation 5-4]

[0161] According to embodiments of the present invention, the chain transfer agent may comprise 97 mol% or more of the organozinc compound represented by Formula 5 above, more preferably 98 mol% or higher, or 99 mol% or higher, and most preferably, it does not contain any by-reaction products other than the organozinc compound. This means that the chain transfer agent, apart from the organozinc compound represented by Formula 5, does not contain any by-reaction products (e.g., dimers) or impurities containing chlorine or magnesium. That is, the chain transfer agent may comprise only the organozinc compound represented by Formula 5 above.

[0162] When ethylene and α-olefin monomers react in the presence of a catalyst composition including a transition metal compound using an organozinc compound represented by Formula 5 as a chain transfer agent, the ethylene and the α-olefin monomer are intercalated between the zinc (Zn) and R10 of the organozinc compound to carry out the polymerization reaction. In one example of the method for preparing the multiblock copolymer of the present invention, when a compound of Formula 4 is used as an organozinc compound to prepare a polyolefin block copolymer by reacting ethylene with an α-olefin monomer, an olefin polymer block intermediate is obtained. An example of this olefin polymer block intermediate can be represented by Formula 6 below.

[0163] [Formula 6]

[0164] In Formula 6 above, R8 and R10 can each be a single bond or a C1 to C10 alkyl group, R9 can be a C1 to C10 alkyl group or -SiR11R12-, R11 and R12 can each be a C1 to C10 alkyl group, and PO can be an olefin polymer block.

[0165] According to an embodiment of the present invention, the organozinc compound can be prepared by a method including preparing a Grignard reagent containing a styrene group and reacting the prepared Grignard reagent with a zinc compound to prepare the organozinc compound represented by Formula 5 above, and the organozinc compound can be an alkyl zinc alkoxide.

[0166] According to embodiments of the present invention, the organozinc compound represented by Formula 5 obtained by the method for preparing organozinc compounds is synthesized as a single compound and therefore does not contain any by-reaction products (e.g., dimers), and furthermore, it does not contain chlorine-containing impurities (which are catalyst poisons, such as organozinc (R-Zn-Cl)). Furthermore, when the organozinc compound represented by Formula 5 is prepared according to the method for preparing organozinc compounds, it is synthesized as a single compound, thus exhibiting excellent synthetic reproducibility. Simultaneously, in order to avoid the presence of by-reaction products and impurities as in the present invention, the key point in preparing the organozinc compound is to select a Grinner reagent containing a styrene group and a zinc compound.

[0167] According to an embodiment of the present invention, the Grinner reagent containing styrene atoms can be represented by the following formula 7.

[0168] [Formula 7]

[0169] In Formula 7 above, R8 and R10 can each be a single bond or a C1 to C10 alkyl group, R9 can be a C1 to C10 alkyl group or -SiR11R12-, R11 and R12 can each be a C1 to C10 alkyl group, and X can be a halogen group.

[0170] Furthermore, according to embodiments of the present invention, in Formula 7 above, R8 and R10 may each be independently a single bond or a C1 to C10 alkyl group, R9 may be a C1 to C10 alkyl group or -SiR11R12-, and R11 and R12 may each be independently a C1 to C10 alkyl group.

[0171] According to an embodiment of the present invention, the styrene-containing GRINM reagent represented by Formula 7 above may be selected from one of the group consisting of GRINM reagents containing styrene-containing GRINM reagents represented by Formulas 7-1 to 7-4 below.

[0172] [Equation 7-1]

[0173] [Equation 7-2]

[0174] [Equation 7-3]

[0175] [Equation 7-4]

[0176] According to an embodiment of the present invention, the Grinner reagent containing a styrene group and represented by Formula 7 above can be prepared by a reaction between a halide (in which a halogen group (-X) is substituted on R8) and magnesium (specifically, magnesium powder or magnesium metal).

[0177] According to an embodiment of the present invention, the Grinner reagent containing styrene atoms and represented by Formula 7 above can be prepared by reacting a compound represented by Formula 8 below with magnesium (specifically, magnesium powder or magnesium metal).

[0178] [Formula 8]

[0179] In Formula 8 above, R8 and R10 can each be a single bond or a C1 to C10 alkyl group, R9 can be a C1 to C10 alkyl group or -SiR11R12-, R11 and R12 can each be a C1 to C10 alkyl group, and X can be a halogen group.

[0180] According to an embodiment of the present invention, in Formula 8 above, R8 and R10 can each be a single bond or a C1 to C3 alkyl group, R9 can be a C1 to C3 alkyl group or -SiR11R12-, R11 and R12 can each be a C1 to C3 alkyl group, and X can be a halogen group.

[0181] Furthermore, according to embodiments of the present invention, in Formula 8 above, R8 and R10 may each be a single bond or a C1 alkyl group, R9 may be a C1 alkyl group or -SiR11R12-, R11 and R12 may each be a C1 alkyl group, and X may be a halogen group selected from the group consisting of Cl, Br, and I.

[0182] According to embodiments of the present invention, the compound represented by Formula 8 above may be selected from one of the groups consisting of compounds represented by Formulas 8-1 to 8-4 below.

[0183] [Equation 8-1]

[0184] [Equation 8-2]

[0185] [Equation 8-3]

[0186] [Equation 8-4]

[0187] According to an embodiment of the present invention, when preparing the styrene-containing Grinner reagent represented by Formula 7 above, the reaction between the compound represented by Formula 8 above and magnesium powder or magnesium metal can be carried out, based on mole percentage, when the mole percentage of magnesium powder or magnesium metal is in excess of 1 mol of the compound represented by Formula 8 above, that is, when the mole percentage is greater than 1 mole, and in this case, 50 mol% or higher, 60 mol% or higher, 70 mol% or higher, 80 mol% or higher, 90 mol% or higher, 95 mol% or higher, or 99 mol% or higher of the compound represented by Formula 8 above can be converted into the styrene-containing Grinner reagent.

[0188] According to embodiments of the present invention, the reaction between the compound represented by Formula 8 and magnesium powder or magnesium metal can be carried out based on a molar ratio, at a molar ratio higher than 1:1 to 1:10, higher than 1:1 to 1:5, higher than 1:1 to 1:2, or 1:1.01 to 1:1.60. Within this range, the conversion to the styrene-containing Grinner reagent represented by Formula 7 is high, and the residual magnesium content after the reaction is minimized, which helps to remove residual magnesium powder or magnesium metal.

[0189] According to embodiments of the present invention, when preparing the organozinc compound, the zinc compound must be a zinc compound capable of inducing the substitution of two (zinc-based) organic groups of the same type. Therefore, zinc chloride (ZnCl₂) is readily considered, but when zinc chloride is used as the zinc compound, there is a problem of leaving chlorine-containing impurities (e.g., alkyl zinc chloride) that can act as catalyst poisons. Therefore, in the present invention, alkyl zinc alkoxides are used as the zinc compound.

[0190] According to embodiments of the present invention, the alkyl group of the alkyl zinc alkoxide may be C1 to C10 alkyl, C1 to C5 alkyl, C1 to C3 alkyl, or ethyl, and the alkoxy group may be C1 to C10 alkoxy, C1 to C5 alkoxy, C1 to C3 alkoxy, or methoxy. As a specific example, the zinc compound may be ethyl zinc methyl oxide.

[0191] According to embodiments of the present invention, the alkyl zinc alkoxide can be prepared from dialkyl zinc. As a specific example, the alkyl zinc alkoxide can be prepared by the on-site reaction of dialkyl zinc with an alcohol. In this case, the alkyl group of the dialkyl zinc can be the same as the alkyl group of the aforementioned alkyl zinc alkoxide, and the alcohol can be an alcohol with hydrogen bonds to the alkoxy group of the aforementioned alkyl zinc alkoxide.

[0192] According to an embodiment of the present invention, when the alkyl zinc alkoxide is used as the zinc compound, magnesium halide alkoxide is generated during the reaction of the Grinner reagent and the zinc compound. This halide is an easily filterable insoluble salt, thus preventing impurity residue.

[0193] According to embodiments of the present invention, the reaction between the Grinner reagent and the zinc compound can be carried out based on a molar ratio of 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, 1.5:1 to 1:1.5, or 1:1. Within this range, the organozinc compound is synthesized as a single compound and therefore does not contain any byproducts, such as dimers, nor chlorine-containing impurities (which can act as catalyst poisons), and has the effect of readily removing magnesium-containing impurities (which can act as catalyst poisons).

[0194] According to embodiments of the present invention, all steps and reactions of the preparation of the zinc compound can be carried out in an organic solvent, and the reaction temperature and reaction pressure can be adjusted to improve the yield and purity.

[0195] According to embodiments of the present invention, the method for preparing the zinc compound uses a Grinner reagent containing a styrene group instead of a boron alkyl compound containing a typical styrene group, and uses an alkyl zinc alkoxide instead of an alkyl zinc or zinc chloride, thus completely removing the catalytic poison.

[0196] Furthermore, by modifying the above method, unlike previous techniques that yielded a mixture of dimers, trimers, and zinc compounds with saturated endpoints as products, it is possible to obtain a single compound in the form of a monomer with fully retained vinyl endpoints. This not only improves the storage stability of the zinc compound but also improves the physical properties of the final compound, and achieves a significantly reduced yield of diblock copolymers compared to triblock copolymers.

[0197] Furthermore, the catalyst composition may further include a compound represented by Formula 9 below, and the compound represented by Formula 8 above may serve as an auxiliary catalyst, a scavenger, or both.

[0198] [Formula 9]

[0199] In Equation 9 above,

[0200] Ra is independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, and

[0201] m is an integer of 2 or greater.

[0202] There are no particular limitations on the compounds represented by Formula 9 above, as long as they are alkylaluminoxanes. Preferred examples include modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., and particularly preferred compounds are modified methylaluminoxane (MMAO).

[0203] The compound represented by Formula 9 above is an oligomer formed by the reaction of alkylaluminum and water. When this compound is used as an auxiliary catalyst, chain transfer is reduced. Therefore, high molecular weight copolymers can be obtained, and the side reaction of homopolymer formation can be prevented. Thus, ultimately, polyolefin-polystyrene multiblock copolymers exhibiting excellent physical properties (e.g., high tensile strength) can be obtained.

[0204] Meanwhile, while the compound represented by Formula 9 can suppress the chain transfer mentioned above, if the compound (e.g., alkylaluminum) is used as an auxiliary catalyst, a large amount of chain transfer occurs, which reduces the molecular weight of the copolymer and increases the formation of homopolymer olefins, leading to a deterioration in the physical properties of the block copolymer.

[0205] As mentioned above, in this invention, a multiblock copolymer that meets the above conditions can be prepared by using a transition metal compound represented by Formula 1 and a compound represented by Formula 9 together.

[0206] Furthermore, the transition metal compounds represented by Formula 1 and the compounds represented by Formula 9 can also be used in a supported form. Silicon oxide or aluminum oxide can be used as the support, but the support is not limited to these.

[0207] Furthermore, the catalyst composition may further include a compound represented by Formula 10 below.

[0208] [Formula 10]

[0209] In Equation 10 above,

[0210] Z is a Group 13 element.

[0211] A is independently an aryl group having 6 to 20 carbon atoms, wherein one or more hydrogen atoms may be substituted by substituents, or an alkyl group having 1 to 20 carbon atoms, and

[0212] The substituent of A is a halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0213] Step (S1) can, for example, be carried out in a homogeneous solution state. In this case, the hydrocarbon solvent or the olefin monomer itself can serve as the medium. The hydrocarbon solvent can be an aliphatic hydrocarbon solvent having 4 to 20 carbon atoms, specifically isobutane, hexane, cyclohexane, methylcyclohexane, etc. The solvent can be used alone or in combination of two or more of them.

[0214] The polymerization temperature in step (S1) can be varied depending on the reactants, reaction conditions, etc., but can specifically be 70 to 170°C, 80 to 150°C, or 90 to 120°C. Within these ranges, the solubility of the polymer can be increased and the catalyst can be thermally stabilized.

[0215] The polymerization reaction in step (S1) can be carried out in a batch, semi-continuous, or continuous manner, and can also be carried out in two or more steps with different reaction conditions.

[0216] The compound obtained by the above step (S1) can be used as a precursor in the anionic polymerization reaction of step (S2) described below to prepare the polyolefin-polystyrene multiblock copolymer of the present invention.

[0217] In one example of the present invention, the α-olefin monomer may be a C5 to C20 α-olefin, and specifically, may be a C5 to C14 α-olefin.

[0218] In one example of the invention, the α-olefin may be selected from one or more of the group consisting of: 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, and 3,4-dimethyl-1-hexene, and more specifically, may be 1-hexene.

[0219] Step (S2)

[0220] Step (S2) is a step of preparing a multiblock copolymer by reacting an aromatic vinyl monomer with a polyolefin block copolymer in the presence of an anionic polymerization initiator.

[0221] In step (S2), aromatic vinyl monomers are continuously inserted between the zinc-carbon bonds of the (polyolefin) 2Zn contained in the compound formed in step (S1), thereby forming a polystyrene chain. Simultaneously, the styrene group derived from the chain extender present at one end of the compound formed in step (S1) can participate as a copolymerization reaction site with the aromatic vinyl monomer to be attached to the polystyrene chain. Furthermore, the multiblock copolymer obtained through the above procedure can be easily quenched by the reaction of the terminal groups with water, oxygen, or organic acids, thereby converting the multiblock copolymer into an industrially useful polyolefin-polystyrene multiblock copolymer.

[0222] The aromatic vinyl monomer can be a C6 to C20 aromatic vinyl monomer. For example, the aromatic vinyl monomer can be an aromatic vinyl monomer including ethylene substituted with C6 to C20 aryl groups, ethylene substituted with phenyl groups, etc., specifically styrene, α-methylstyrene, vinyltoluene, alkylstyrene substituted with C1-3 alkyl groups (e.g., o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, etc.) or halogen-substituted styrene, and more specifically styrene.

[0223] In one example of the present invention, the anionic polymerization initiator may be an alkyl lithium compound represented by Formula 11 below.

[0224] [Equation 11]

[0225] In Equation 11 above,

[0226] R 13 is hydrogen or a C1 to C20 hydrocarbon, and

[0227] Am refers to amine compounds represented by the following formula 12.

[0228] [Equation 12]

[0229] In Equation 12 above,

[0230] R14 to R18 are each independently hydrogen or C1 to C20 hydrocarbons, and

[0231] a and b are each independent integers from 0 to 3, where a and b are not both 0 at the same time.

[0232] In one example of the present invention, R 13 may be hydrogen, C1 to C20 alkyl, C3 to C20 cycloalkyl, or substituted or unsubstituted C7 to C20 arylalkyl.

[0233] R14 to R18 may each be independently hydrogen, C1 to C20 alkyl, C1 to C20 alkenyl, C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C7 to C20 aralkyl, and

[0234] a and b can each be an integer from 0 to 2 independently.

[0235] Furthermore, in one example of the present invention, R13 to R18 may each be independently hydrogen or C1 to C20 alkyl, wherein a may be 1 or 2, and b may be 0 or 1.

[0236] Specifically, a can be an integer from 1 to 3, and b can be an integer from 0 to 3. More specifically, a can be 1 or 2, and b can be an integer from 0 to 2. More specifically, a can be 1 or 2, and b can be 0 or 1.

[0237] In one example of the present invention, Am in the above formula 11 can be specifically represented by the following formula 13 or 14.

[0238] [Equation 13]

[0239] [Formula 14]

[0240] In the above formula,

[0241] R14, R15, and R18 are each independently hydrogen or C1 to C20 alkyl.

[0242] Furthermore, in one example of the present invention, Am in the above formula 11 can be specifically represented by the following formula 13a or formula 14a.

[0243] [Equation 13a]

[0244] [Equation 14a]

[0245] In the method for preparing the multiblock copolymer of the present invention, the compound represented by Formula 11 above is used as an initiator for anionic polymerization. Therefore, polystyrene chains can be grown from the polyolefin chains obtained in step S1, which have grown near the organozinc compound (especially zinc (Zn)). As described above, in the method for preparing the multiblock copolymer of the present invention, polystyrene-polyolefin-polystyrene multiblock copolymers can be obtained by growing polystyrene chains at both ends of the polyolefin chains. Therefore, the obtained multiblock copolymer can have a nearly symmetrical structure and can have a uniform polystyrene block size.

[0246] This anionic polymerization initiator can be prepared by the following method.

[0247] The method for preparing the anionic polymerization initiator includes a procedure of introducing a compound represented by Formula 16 and a compound represented by Formula 12 in the presence of the compound represented by Formula 15 below and carrying out a reaction.

[0248] [Equation 12]

[0249] [Formula 15]

[0250] [Formula 16]

[0251] In the above formula,

[0252] R13 to R18 are each independently hydrogen or C1 to C20 hydrocarbons.

[0253] a and b are each independent integers from 0 to 3, where a and b are not both 0 at the same time.

[0254] B is a C1 to C20 alkyl group.

[0255] In one example of the present invention, R 13 may be hydrogen or a C1 to C20 hydrocarbon, R 14 to R 18 may each independently be hydrogen, a C1 to C20 alkyl, a C1 to C20 alkenyl, a C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C20 aryl, or a substituted or unsubstituted C7 to C20 aralkyl, and a and b may each independently be an integer from 0 to 2, and B may be a C1 to C12 alkyl.

[0256] Furthermore, in one example of the present invention, R14 to R18 may each be independently hydrogen or C1 to C20 alkyl, a may be an integer of 1 or 2, b may be an integer of 0 or 1, and B may be C1 to C8 alkyl.

[0257] Specifically, a can be an integer from 1 to 3, and b can be an integer from 0 to 3. More specifically, a can be 1 or 2, and b can be an integer from 0 to 2. More specifically, a can be 1 or 2, and b can be 0 or 1.

[0258] The alkyl lithium compound represented by Formula 16 above can be, for example, n-BuLi, wherein n-BuLi is a material widely used as an initiator for anionic polymerization reactions, and is readily available and has excellent cost-effectiveness per unit.

[0259] In the preparation of anionic polymerization initiators, the reaction of the compound represented by Formula 16 with the compound represented by Formula 15 can be performed first, and then the compound can be reacted with the compound of Formula 12 to obtain the compound of Formula 11. Specifically, the compound represented by Formula 16 reacts with the compound represented by Formula 15 to obtain an allyllithium intermediate, and the allyllithium reacts with the compound of Formula 12 to finally form the anionic polymerization initiator of Formula 11.

[0260] Furthermore, the procedure of introducing the compounds represented by Formula 16 and Formula 12 in the presence of the compound represented by Formula 15 can be carried out under conditions without additional solvent. The condition without additional solvent means that, in the presence of the compound represented by Formula 16, no other compound is used as a solvent besides the compounds represented by Formula 15 and Formula 12, or that only trace amounts of additional solvent are present, and therefore do not react significantly with the compound represented by Formula 15.

[0261] When the reaction is carried out without additional solvent, the reaction between the compound represented by Formula 15 and the compound represented by Formula 16 is the main reaction, thus the anionic polymerization initiator of Formula 11 can be obtained efficiently. When a separate solvent is present, the anionic polymerization initiator of Formula 11, the compound obtained by reacting the compound represented by Formula 15 with the compound represented by Formula 12, and the compound derived from the decomposition of the compound obtained by reacting the compound represented by Formula 15 with the compound represented by Formula 12 all mix and exist, thus resulting in inefficiency.

[0262] [Example]

[0263] The present invention will be described in detail below with reference to examples. However, the following examples are merely illustrative and are not intended to limit the scope of the invention.

[0264] [Reagents and Experimental Conditions]

[0265] All experiments were conducted under inert gas conditions using a standard glove box and the Schlenk technique. Toluene, hexane, and tetrahydrofuran (THF) were used after distillation with benzophenone radicals (anionic). Methylcyclohexane (anhydrous grade) used for polymerization was purchased from Tokyo Chemical Industry (TCI) and purified with Na / K alloy before use. Sublimation grade HfCl4 was purchased from Streme and used in its virgin state. Ethylene-propylene gas mixtures were purified with trioctylaluminum (0.6 M, in a mineral oil system) in a bomb reactor (2.0 L) before use.

[0266] ¹H NMR (600 MHz) and ¹³C NMR (150 MHz) spectra were recorded using an ECZ 600 instrument (JEOL).

[0267] GPC data were analyzed in 1,2,4-trichlorobenzene at 160 °C using a PL-GPC 220 system equipped with a refractive index detector and two columns (PLarian Mixed-B 7.5 × 300 mm Varian [Polymer Lab]).

[0268] [Preparation Example]

[0269] (1) Preparation of transition metal compounds

[0270] [Equation 1-1]

[0271] (i) Preparation of coordination compound

[0272]

[0273] 2,6-Dicyclohexylaniline (0.772 g, 3.00 mmol) and 6-bromo-2-pyridinecarboxaldehyde (0.558 g, 3.00 mmol) were dissolved in toluene (5 mL) with molecular sieves added. The mixture was heated to 70 °C overnight with stirring. After filtration, the solvent was removed using a rotary evaporator. A yellow solid (1.07 g, 84%) was given.

[0274] 1H NMR (C 6D 6): δ 8.41 (s, 1H, NCH), 8.09 (d, J= 7.8 Hz, 1H), 7.53 (m, 3H), 6.85 (d, J= 7.8 Hz, 1H), 6.63 (t, J= 7.8 Hz, 1H), 2.74 (m, 2H), 1.87 (d, J= 12 Hz, 4H), 1.64 (d, J= 12.6 Hz, 4H), 1.54 (d, J= 10.8 Hz, 2H), 1.39 (quartet, J= 10.2 Hz, 4H), 1.11 (m, 6H) ppm.

[0275] 13C NMR (C 6D 6): δ 26.55, 27.33, 34.25, 39.30, 119.42, 124.32, 125.21, 129.83, 136.68, 138.82, 142.54, 148.94, 155.95, 162.06ppm.

[0276] HRMS (EI): Theoretical m / z value ([M+]C24H29BrN2) 424.1514. Experimental value: 424.1516.

[0277] Under nitrogen atmosphere, the compound (1.07 g, 2.51 mmol), 1-naphthylboronic acid (0.453 g, 2.64 mmol), Na₂CO₃ (0.700 g, 6.60 mmol), and toluene (5 mL) were packed into a Schlenk flask. A solution of (Ph₃P)₄Pd (7.83 mg, 0.00678 mmol) in degassed H₂O / EtOH (1 mL, v / v, 1:1) and toluene (1 mL) was added. Column chromatography on silica gel with ethyl acetate (v / v, 90:3:1) containing hexane and a small amount of triethylamine gave a pale yellow oil (0.712 g, 60%).

[0278] 1H NMR (C 6D 6): δ 8.70 (s, 1H, NCH), 8.41 (d, J= 7.8 Hz, 1H), 8.31 (d, J= 7.8 Hz, 1H), 7.68 (d, J= 7.2 Hz, 1H), 7.65 (d, J= 7.8 Hz, 1H), 7.54 (d, J= 7.2 Hz, 1H), 7.27 (m, 4H), 7.20 (m, 4H), 2.93 (m, 2H), 1.90 (d, J= 12 Hz, 4H), 1.61 (d, J= 13.2 Hz, 4H), 1.50 (d, J= 12.6 Hz, 2H), 1.38 (m, 4H), 1.11 (m, 6H), ppm.

[0279] 13C NMR (C 6D 6): δ 26.63, 27.38, 34.35, 39.36, 119.21, 124.32, 124.98, 125.50, 126.15, 126.21, 126.64, 126.75, 128.15, 128.73, 129.38, 131.81, 134.52, 136.94, 137.14, 138.52, 149.48, 155.13, 159.79, 164.05 ppm.

[0280] HRMS(EI): Theoretical m / z value ([M+]C34H36N2) 472.2878. Experimental value: 472.2878.

[0281] 2-Isopropylphenyllithium (0.114 g, 0.904 mmol) dissolved in diethyl ether (8 mL) was added dropwise to a Schlenk flask containing the compound (0.247 g, 0.523 mmol) in diethyl ether (20 mL). The mixture was stirred for 3 hours, then an aqueous solution of ammonium chloride (0.30 g) (10 mL) was added. The product was extracted with diethyl ether (3 × 10 mL). The resulting oil was dried overnight under high vacuum at 60 °C. A yellow solid (0.257 g, 83%) was given.

[0282] 1H NMR (C 6D 6): δ 8.24 (m, 1H), 7.90 (m, 1H), 7.64 (m, 1H), 7.62 (d, J= 7.8 Hz, 1H), 7.56 (d, J= 7.2 Hz, 1H), 7.26 (m, 3H), 7.22 (m, 4H), 7.11 (m, 5H), 5.62 (d, J= 5.4 Hz, 1H, NCH), 4.59 (d, J= 5.4 Hz, 1H, NH), 3.31 (septet, J= 7.2 Hz, 1H,CH), 2.74 (m, 2H), 1.79 (d, J= 7.8 Hz, 2H), 1.64 (m, 4H), 1.54 (m, 4H), 1.32 (m, 4H), 1.08 (m, 2H), 1.03 (d, J= 6.6 Hz, 3H, CH 3), 1.00 (m, 1H), 0.980 (d, J= 6.6 Hz, 3H, CH 3), 0.921 (m, 3H)ppm.

[0283] 13C NMR (C 6D 6): δ 23.78, 24.45, 26.63, 27.42, 27.54, 28.96, 34.77, 35.08, 39.01, 67.64, 119.99, 122.89, 124.13, 124.80, 125.36, 125.77, 126.08, 126.46, 126.56, 126.71, 127.58, 128.55, 129.35, 131.84, 134.64, 136.94, 138.77, 141.88, 142.24, 144.97, 146.32, 159.28, 163.74 ppm.

[0284] HRMS(EI): Theoretical m / z value ([M+]C43H48N2) 592.3817. Experimental value: 592.3819.

[0285] (ii) Preparation of transition metal compounds

[0286] [Equation 1-1]

[0287] A coordinating compound (0.150 g, 0.253 mmol) in toluene (1.5 g) was packed into a Schlenk flask, and n-BuLi (0.17 mL, 1.6 M solution in toluene, 0.27 mmol) was added dropwise at room temperature. The mixture was stirred for 1 hour, followed by the addition of solid HfCl₄ (0.0814 g, 0.254 mmol). The reaction mixture was heated at 100 °C and stirred for 2 hours. After cooling, MeMgBr (0.29 mL, 3.1 M solution in diethyl ether, 0.89 mmol) was added, and the mixture was stirred overnight at room temperature. After removing volatiles under vacuum, the product was extracted with toluene (1.5 g). The extract was obtained by filtration through a cellite filter. After removing the solvent under vacuum, the residue was softened in hexane (2 mL) to give a yellow solid (0.128 g, 63%).

[0288] 1H NMR (C 6D 6): δ 8.58 (d, J = 7.8 Hz, 1H), 8.29 (d, J = 8.4 Hz, 1H), 7.79 (d, J = 7.8 Hz, 1H), 7.71 (d, J= 7.2 Hz, 1H), 7.54 (d, J= 7.8 Hz, 1H), 7.46 (m, 1H), 7.30 (m, 2H), 7.15 (m, 3H), 7.09 (m, 3H), 6.88 (t, J= 7.8 Hz, 1H), 6.62 (d, J= 8.4 Hz, 1H), 6.48 (s, 1H, NCH), 3.39 (m, 1H), 2.92 (m, 2H), 2.15 (d, J= 13.8 Hz, 1H), 2.10 (d, J= 13.8 Hz, 2H), 1.80 (m, 2H), 1.65 (m, 3H), 1.29 (m, 6H), 1.17 (d, J= 7.2 Hz, 3H, CH 3), 1.07 (m, 3H), 0.99 (s, 3H, HfCH 3), 0.95 (m, 2H), 0.73 (d, J= 7.2 Hz, 3H, CH 3), 0.70 (s, 3H, HfCH 3), 0.23 (m, 1H) ppm。

[0289] 13C NMR (C 6D 6): δ 23.31, 25.04, 26.63, 26.74, 27.70, 27.76, 27.81, 28.29, 28.89, 35.00, 35.66, 36.62, 37.02, 38.13, 40.88, 62.53, 67.00, 77.27, 119.30, 120.30, 124.29, 125.52, 125.60, 125.97, 126.95, 127.06, 127.73, 129.91, 130.00, 130.09, 130.85, 134.36, 135.80, 140.73, 140.89, 144.02, 145.12, 146.31, 146.38, 146.49, 164.46, 170.79, 206.40 ppm。

[0290] Analysis. Theoretical values ​​(C 45H 52HfN 2): C, 67.61; H, 6.56; N, 3.50%. Calculated values: C, 67.98; H, 6.88; N, 3.19%.

[0291] (2) Preparation of organozinc compounds

[0292] 15.0 g (98.3 mmol) of 4-vinylbenzyl chloride and 2.628 g (108.1 mmol) of magnesium metal were added to 78 mL of diethyl ether and stirred at 0 °C for 1.0 h. The mixture was then filtered through Serry media to remove excess magnesium. 19.2 g (81.9 mmol) of p-toluenesulfonyl-OCH₂CH₂Cl was dissolved in 27 mL of diethyl ether and added dropwise to the prepared 4-vinylbenzyl-magnesium chloride (4-vinylbenzyl-MgCl) Grignard reagent. The mixture was stirred overnight and then filtered through Serry media to remove toluenesulfonyl magnesium chloride (MgCl(OTs)), which is an insoluble salt. The filter cake was washed three times with 70 mL of hexane, and the solvent was removed by a rotary evaporator to give 14.2 g of crude product. 43 mg (3,000 ppm) of tertiary butylcatechol was added as a free radical scavenger, and vacuum distillation was performed at 85 °C under full vacuum to give the compound represented by Formula 8-4-1. The weight of the obtained compound was measured, and the yield was 81% by weight. ¹H NMR and ¹³C NMR spectra were measured.

[0293] [Equation 8-4-1]

[0294] 1H NMR (C 6D 6): δ 7.20 (d, J = 8.4 Hz, 2H), 6.88 (d, J = 8.4 Hz, 2H), 6.61 (dd, J = 16, 9.6 Hz, 1H, =CH), 5.63 (d, J = 16 Hz, 1H, =CH 2), 5.09 (d, J = 9.6 Hz, 1H, =CH 2), 3.04 (t, J = 6.6 Hz, 2H, CH 2), 2.42 (t, J = 6.6 Hz, 2H, CH 2), 1.64 (quintet, J = 6.6 Hz, 2H, CH 2Cl) ppm.

[0295] 13C NMR (C 6D 6): δ 32.61, 34.12, 44.07, 113.13, 126.74, 128.97, 135.99, 137.11, 140.63 ppm.

[0296] Subsequently, 10.0 g (55.3 mmol) of the compound (4-(3-chloropropyl)styrene) prepared as indicated in 8-4-1 above was dissolved in a mixed solvent of 20 mL toluene and 7.98 g (111 mmol) tetrahydrofuran (THF), and added dropwise to a suspension of 2.02 g (83.0 mmol) magnesium powder in 40 mL toluene under stirring at room temperature. After stirring for 5.0 h, a slight heat was gradually generated, and the reaction mixture was then filtered through Seryne filter media to remove excess magnesium. 6.94 g (55.3 mmol, 1 equivalent relative to Grinner's reagent) of ethyl zinc methyl methoxide (prepared by reacting 6.83 g (55.3 mmol) of diethylzinc (Et 2Zn) and 1.78 g (55.3 mmol) of methanol in 30 mL toluene at room temperature for 1.0 h) was added to the filtrate. Then, 60 ml of toluene was added, followed by stirring at room temperature for 1.0 h, and the solvent was removed using a high vacuum line. Next, 96 g of hexane was added, and magnesium chloride methyl oxychloride (MgCl(OMe)), an insoluble salt, was removed on a Seryne filter. The filtrate was stored at -30 °C to allow the compound represented by formula 5-4 to deposit as a white crystalline solid. The yield was measured to be 56 wt% (7.28 g), and ¹H NMR and ¹³C NMR were measured.

[0297] [Equation 5-4]

[0298] 1H NMR (C 6D 6): δ 7.24 (d, J = 7.8 Hz, 2H), 6.90 (d, J = 7.8 Hz, 2H), 6.64 (dd, J = 17, 11 Hz, 1H, =CH), 5.66 (d, J = 17 Hz, 1H, =CH 2), 5.11 (d, J = 11 Hz, 1H, =CH 2), 2.43 (t, J = 7.2 Hz, 2H, CH 2), 1.80 (quintet, J = 7.2 Hz, 2H, CH 2), -0.19 (t, J = 7.2 Hz, 2H, CH 2Zn) ppm.

[0299] 13C NMR (C 6D 6): δ 12.66, 28.82, 40.09, 113.15, 127.31, 129.23, 136.05, 137.10, 142.91 ppm.

[0300] (3) Preparation of anionic polymerization initiators

[0301]

[0302] n-BuLi (0.14 mg, 2.2 mmol) was added dropwise to pentamethyldiethyltriamine (PMDTA, 0.37 g, 2.2 mmol) in 1-octene (13.0 g). The mixture was stirred overnight at room temperature to obtain a yellow solution of pentylallyl-Li·(PMDTA) (0.16 mmol-Li / g). A portion of the solution was analyzed by 1H NMR spectroscopy. The 1H NMR spectrum was recorded, followed by quenching the C6D6 solution with H2O (or D2O), filtering through a short pad of anhydrous MgSO4 in a pipette, and recording the 1H NMR spectrum again.

[0303] [Polyolefins] [-] Preparation of polystyrene-based multiblock copolymers

[0304] [Example] [1]

[0305] A Parr reactor (3.785 L) was dried under vacuum at 120 °C for 2 hours. A solution of MMAO (0.6 mg, 1,000 μmol-Al) as a scavenging agent in methylcyclohexane (1,200 g) was introduced into the reactor, and the mixture was stirred at 120 °C for 1 hour using a heating jacket. After that, the solution was removed using a sleeve.

[0306] The reactor was filled with methylcyclohexane (1,200 g) containing MMAO (1,000 μmol-Al) as a scavenging agent, and 1-hexene (560 g) as an α-olefin monomer, and the temperature was set to 90°C. A solution of the organozinc compound (3,100 μmol) of formula 5-4 in methylcyclohexane (5 g) was then injected as a chain transfer agent, followed by an injection of a methylcyclohexane solution containing a transition metal compound (12 μmol-Hf) activated by [(C18H37)2N(H)Me]+[B(C6F5)4]-(1.0 equivalent) in methylcyclohexane. The polymerization reaction was carried out for 40 minutes in the range of 90 to 120°C, while the pressure in the reactor was maintained at 25 bar by opening the valve of the ethylene tank. After the polymerization reaction, the ethylene gas was vented, and the temperature of the reactor was then adjusted back to 90°C.

[0307] At 90°C, pentylallyl-Li·(PMDTA) (2,600 μmol) was added to methylcyclohexane (10 g). While stirring, the temperature was maintained at 90°C for 30 minutes, followed by the injection of styrene (104 g). The temperature was adjusted to 90-100°C using a heating mantle. Within 5 hours, the viscosity gradually increased and became almost invisible. A portion was obtained for analysis using 1H NMR spectroscopy. 1H NMR analysis of a portion confirmed complete styrene conversion. After complete styrene conversion, 2-ethylhexanoic acid and ethanol were continuously injected. The resulting polymer was dried overnight in a vacuum oven at 80°C.

[0308] [Example] [2] [to] [4]

[0309] Multiblock copolymers were prepared in the same manner as in Example 1, but the reaction conditions were changed to those shown in Table 1 below.

[0310] [Comparative Example] [1]

[0311] G1651, which is a SEBS of Kraton Inc., for example, Comparative Example 5.

[0312] [Comparative Example] [2]

[0313] Multiblock copolymers were prepared in the same manner as in Example 1, but diethylzinc was used instead of the organozinc compound of formula 5-4 in Example 1, and the reaction conditions were changed to those shown in Table 1 below.

[0314] [Comparative Example] [3]

[0315] Me3SiCH2Li (2,600 μmol, 291.4 mg) and PMDETA (2,600 μmol, 537.3 mg) were mixed with methylcyclohexane (20.7 g) and then stirred at room temperature for 30 minutes to prepare a polymerization initiator.

[0316] Multiblock copolymers were prepared in the same manner as in Example 1, but the above-prepared Me 3SiCH 2Li·(PMDETA) was used instead of pentylallyl-Li·(PMDTA) as the anionic initiator in Example 1, and the reaction conditions were changed to those shown in Table 1 below.

[0317] [Comparative Example] [4]

[0318] Multiblock copolymers were prepared in the same manner as in Example 1, but Oc 3Al (1976.7 mg, 1,348 μmol-Al / 25 wt% in hexane) was used instead of MMAO as the scavenger in Example 1, and the reaction conditions were changed to those shown in Table 1 below.

[0319] [Comparative Example] [5]

[0320] According to the preparation of transition metal compounds, auxiliary catalysts, and organozinc compounds described in Korean Patent Publication 2020-0132635, transition metal compounds, auxiliary catalysts, and organozinc compounds are prepared, and then polyolefin-polystyrene multiblock copolymers are prepared according to the method described in Example 1 of Korean Patent Publication 2020-0132635.

[0321] []

[0322] [Experimental Example] [1] []

[0323] The physical properties of the polyolefin-polystyrene multiblock copolymers of the examples and comparative examples are measured as follows.

[0324] (1) Measurement of the content of ethylene, α-olefins and styrene

[0325] Measurements were performed using nuclear magnetic resonance (NMR). A Bruker 600MHz AVANCE III HD NMR system was used. ¹H NMR was measured at ns=16, d1=3s, solvent=TCE-d2, and 373K, with the TCE-d2 solvent peak corrected to 6.0 ppm. The CH₃-correlation peaks (triples) of 1-propylene at 1 ppm and the CH₃-correlation peaks of the butyl branch of 1-hexene at approximately 0.96 ppm were confirmed, and the content was calculated accordingly. Additionally, the styrene content was calculated using aromatic peaks at approximately 6.5 to 7.5 ppm.

[0326] (2) Weight-average molecular weight (Mw, g / mol) and dispersion index (PDI)

[0327] The weight-average molecular weight (Mw, g / mol) and number-average molecular weight (Mn, g / mol) were measured by gel permeation chromatography (GPC), and the polymer dispersion index (PDI) was calculated by dividing the weight-average molecular weight by the number-average molecular weight.

[0328] - Column: PL Olexis

[0329] - Solvent: TCB (trichlorobenzene)

[0330] - Flow rate: 1.0 ml / min

[0331] - Sample concentration: 1.0 mg / ml

[0332] - Injection volume: 200 mm

[0333] - Column temperature: 160℃

[0334] - Detector: Agilent high-temperature RI detector

[0335] - Standard product: Polystyrene

[0336] - The molecular weight was calculated using the Mark-Houwink equation (K = 40.8 × 10⁻⁵, α = 0.7057) with universal calibration.

[0337] (3) Measurement of the slope of the G'-G” graph

[0338] Using a Dynamic Mechanical Analysis (DMA) apparatus, the temperature was increased from 130°C to 250°C at a rate of 5°C per minute, at a frequency of 1 Hz and a strain of 0.5%. The storage modulus G' and the loss modulus G” based on temperature were obtained, and then plotted with the storage modulus G' and the loss modulus G” based on temperature as the y-axis and x-axis, respectively. Figure 1 shows the G'-G” plot for Example 2. In addition, Figure 2 shows the slope values ​​of the storage modulus at each temperature in the example and comparative examples.

[0339]

[0340] [Experimental Example] [2]

[0341] According to the tensile testing method of ASTM D412, specimens were prepared using the block copolymers of the examples and comparative examples, and the tensile strength, elongation, and 300% modulus of each specimen were measured.

[0342] The results are shown in Table 3.

[0343] Furthermore, the strain was measured based on the stress applied to each specimen, and the stress-strain diagram with elongation as the x-axis and tensile strength as the y-axis is shown in Figure 3.

[0344] []

[0345] As shown in Table 3, the block copolymers of the examples have excellent tensile strength and elongation, and also exhibit an appropriate degree of 300% modulus value. Therefore, it can be confirmed that all tensile properties are significantly higher than those of the comparative examples that do not meet all the above conditions.

[0346] Meanwhile, referring to Figure 3, there are differences between the stress-strain curves of the block copolymers of the examples and the block copolymers of the comparative examples. Specifically, the block copolymers of the comparative examples exhibit significantly higher strain values ​​in response to applied stress than the block copolymers of the examples, while the block copolymers of the examples exhibit lower strain values ​​in response to applied stress. In particular, it can be confirmed that the strain gradually decreases after a predetermined amount of stress is increased.

[0347] The above results confirm that the multiblock copolymer of the present invention has excellent tensile strength and elongation and also exhibits an appropriate degree of 300% modulus, resulting in excellent tensile properties.

Claims

1. A multiblock copolymer comprising polystyrene blocks including repeating units derived from aromatic vinyl monomers, and polyolefin blocks including repeating units derived from ethylene and repeating units derived from α-olefin monomers, wherein when plotted using temperature-dependent storage modulus G' and temperature-dependent loss modulus G” as measured by dynamic mechanical analysis as the y-axis and x-axis, respectively, the multiblock copolymer satisfies the following conditions: a) a slope of 2.00 to 4.00 at 130°C, and b) a slope of 3.00 to 5.00 at 190°C.

2. The multiblock copolymer of claim 1, wherein the α-olefin is selected from one or more of the group consisting of: 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, and 3,4-dimethyl-1-hexene.

3. The multiblock copolymer of claim 1, wherein the slope of the multiblock copolymer at 130°C is lower than the slope at 190°C.

4. The multiblock copolymer of claim 1, wherein the multiblock copolymer further meets condition c): the difference between the slope at 130°C and the slope at 190°C is 0.50 to 2.

00.

5. The multiblock copolymer of claim 1, wherein the multiblock copolymer further conforms to a slope in the range of 2.00 to 5.00 within the range of 130°C to 250°C.

6. The multiblock copolymer of claim 1, wherein the multiblock copolymer further meets the condition of a slope of 3.00 to 4.80 at 250°C.

7. The multiblock copolymer of claim 1, wherein the molecular weight distribution of the multiblock copolymer is from 1.5 to 3.0 as measured by gel permeation chromatography (GPC).

8. A method for preparing a multiblock copolymer as claimed in claim 1, the method comprising: (S1) reacting ethylene with an α-olefin monomer to prepare a polyolefin block copolymer in the presence of a catalyst composition including a transition metal compound, using an organozinc compound as a chain transfer agent; and (S2) reacting the polyolefin block copolymer with an aromatic vinyl monomer in the presence of an anionic polymerization initiator to prepare a multiblock copolymer, wherein the transition metal compound is a compound represented by the following formula 1: wherein in the above formula 1, M is Ti, Zr, or Hf, R1 to R4 are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl, two or more of which may be linked together and form a ring. R5 and R6 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, or a substituted or unsubstituted C6 to C20 aryl, wherein the substitution is a C1 to C12 alkyl substitution, and R7 is each independently substituted or unsubstituted C4 to C20 alkyl, a substituted or unsubstituted C4 to C20 cycloalkyl, or a substituted or unsubstituted C6 to C20 aryl. n is 1 to 5, and Y1 and Y2 are each independently a halogen, substituted or unsubstituted C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, C7 to C20 aralkyl, C5 to C20 heteroaryl, C1 to C20 alkoxy, substituted or unsubstituted C5 to C20 aryloxy, C1 to C20 alkylamino, C5 to C20 arylamino, C1 to C20 alkylthio, C5 to C20 arylthio, C1 to C20 alkylsilyl, C5 to C20 arylsilyl, hydroxyl, amino, thio, silyl, cyano, or nitro.

9. The method of claim 8, wherein the organozinc compound is represented by the following formula 5: wherein in the above formula 5, R8 and R10 are each independently a single bond or a C1 to C10 alkyl group, R9 is a C1 to C10 alkyl group or -SiR11R12-, and R11 and R12 are each independently a C1 to C10 alkyl group.

10. The method of claim 9, wherein the organozinc compound is prepared by reacting a Grignard reagent containing a styrene group with an alkyl zinc alkoxide.

11. The method of claim 10, wherein the Grinner reagent containing the styrene group is represented by the following formula 7: wherein in the above formula 7, R8 and R10 are each independently a single bond or a C1 to C10 alkyl group, R9 is a C1 to C10 alkyl group or -SiR11R12-, R11 and R12 are each independently a C1 to C10 alkyl group, and X is a halogen group.

12. The method of claim 8, wherein the anionic polymerization initiator comprises an alkyl lithium compound containing an allyl group, wherein the allyl group is incorporated with lithium.

13. The method of claim 12, wherein the alkyllithium compound is represented by the following formula 11: wherein in the above formula 11, R13 is hydrogen or a C1 to C20 hydrocarbon, and Am is an amine compound represented by the following formula 12: wherein in the above formula 12, R14 to R18 are each independently hydrogen or a C1 to C20 hydrocarbon, and a and b are each independently integers from 0 to 3, wherein a and b are not simultaneously 0.

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