TW202330682A - Multi-block copolymer and method for preparing the same - Google Patents

Abstract

The present invention relates to a multi-block copolymer including a polystyrene-based block and a polyolefin-based block, and having a high molecular weight and a low content of homo-polystyrene, and a method for producing the multi-block copolymer.

Description

Multi-block copolymer and its production method

The present invention relates to multi-block copolymers and methods for their manufacture, and in particular to polyolefin-polystyrene multi-block copolymers comprising polystyrene blocks and polyolefin blocks, and to the manufacture of The method of the multi-block copolymer.

Cross-reference to related applications

This application claims the rights and interests of Korean Patent Application No. 10-2021-0130752 filed on October 1, 2021, which is hereby incorporated by reference in its entirety.

The block copolymer is a material widely used not only in everyday-use plastics but also in high-tech devices, and thus research and development thereof are actively conducted. In particular, styrene-olefin copolymer resins including both polyolefin-based (POs) blocks and polystyrene-based (PSs) blocks have excellent properties such as heat resistance, light resistance, elasticity, etc., and thus It can be usefully used in various technical fields.

Polyolefin-polystyrene block copolymers such as styrene-ethylene-butylene-styrene (SEBS) or styrene-ethylene-propylene-styrene (SEPS) currently have a global market of several hundred thousand tons. A representative example of the styrene-olefin copolymer resin may be polystyrene-block-poly(ethylene-co-1-butene)-block-polystyrene (SEBS) triblock copolymer. The SEBS triblock copolymer exhibits thermoplastic elasticity due to the separation of hard polystyrene blocks in the structure from the soft poly(ethylene-co-1-butene) matrix and serving as physical crosslinking points. Because of these properties, SEBS is more widely used in product groups requiring rubber and plastics, and with the gradual expansion of its use range, the demand for SEBS has increased significantly.

[Prior Art Literature]

[Patent Document]

(Patent Document 1) Korean Patent Publication No. 10-1657925

Want to solve technical problems

One aspect of the present invention proposes a multi-block copolymer comprising polystyrenic blocks and polyolefin-based blocks, and more particularly, provides a polyolefin-polyethylene copolymer having a high molecular weight and a low content of homopolystyrene Styrenic multi-block copolymer. technical means to solve problems

According to one aspect of the present invention, a multi-block copolymer and a method for producing the multi-block copolymer are proposed.

(1) The present invention proposes a multi-block copolymer comprising polystyrene-based blocks including repeating units derived from aromatic vinyl-based monomers and repeating units derived from ethylene and α-olefin-based A polyolefin-based block of repeating units of monomers, wherein the polystyrene homopolymer measured by gel permeation chromatography (GPC) relative to the polystyrene-based block expressed by the following equation 1 The fraction is 4% or less, and the weight average molecular weight (MW) measured by gel permeation chromatography (GPC) is 100,000 to 300,000 g/mol.

[equation 1] Homopolymer fraction (area%)=area of homopolystyrene peak∕(area of polystyrene block peak+area of homopolystyrene peak)×100(%)

(2) In the above (1), the present invention proposes a multi-block copolymer, wherein the α-olefin monomer system is selected from one or more of the following groups: 1-hexene, 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) In the above (1) or (2), the present invention proposes a multi-block copolymer, wherein the polystyrene homopolymer measured by the gel permeation chromatography (GPC) is relative to the polystyrene The fraction of series blocks is 3.80% or less.

(4) In any one of (1) to (3) above, the present invention provides a multi-block copolymer wherein the molecular weight distribution measured by the gel permeation chromatography (GPC) is 1.5 to 3.0.

(5) In any one of the above (1) to (4), the present invention proposes a multi-block copolymer, wherein by ¹ H NMR (500 MHz, tetrachloroethane-d2, standard TMS) spectrum measurement , the content of the repeating unit derived from an α-olefin-based monomer is 10 mol% to 20 mol%.

(6) In any one of the above (1) to (5), the present invention proposes a multi-block copolymer, wherein by ¹ H NMR (500 MHz, tetrachloroethane-d2, standard TMS) spectrum measurement , the content of the repeating unit derived from an α-olefin-based monomer is 20% by weight to 40% by weight.

(7) The present invention proposes a method for producing a multi-block copolymer, which method includes (S1) using an organozinc compound as a chain transfer agent, in the presence of a catalyst composition including a transition metal compound, by ethylene and α-olefin Reaction of monomers to prepare polyolefin-based blocks; and (S2) in the presence of anionic polymerization initiators, the reaction of aromatic vinyl-based monomers and polyolefin-based blocks to produce multi-block copolymers .

(8) In the above (7), the present invention proposes a method for producing a multi-block copolymer, wherein the transition metal compound is a compound represented by the following formula 1.

[Formula 1]

In the above formula 1,

M is Ti, Zr, or Hf,

R ₁ to R ₄ 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 aromatic group, wherein two or more adjacent ones can be connected to each other and form a ring,

R ₅ and R ₆ 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 aromatic group, wherein the substitution is carried out with a C1 to C12 alkyl group,

_Each R is independently substituted or unsubstituted C4 to C20 alkyl, substituted or unsubstituted C4 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl,

n is 1 to 5, and

Y and Y _are each independently halo, 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 alkaryl, 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 base.

(9) In the above (7) or (8), the present invention proposes a method for producing a multi-block copolymer, wherein the organozinc compound is represented by the following formula 5.

[Formula 5]

In the above equation 5,

R ₈ and R ₁₀ are each independently a single bond or C1 to C10 alkylene, R ₉ is C1 to C10 alkylene or -SiR ₁₁ R ₁₂ -, and R ₁₁ and R ₁₂ are each independently C1 to C10 alkylene base.

(10) In any one of the above (7) to (9), the present invention proposes a method for producing a multi-block copolymer, wherein the organozinc compound is prepared from a Grignard reagent containing a styrene moiety and an alkane Prepared by the reaction of zinc-based alkoxides.

(11) In any one of (7) to (11) above, the present invention proposes a method for producing a multi-block copolymer, wherein the Grignard reagent containing a styrene moiety is represented by the following formula 7.

[Formula 7]

In the above equation 7,

R ₈ and R ₁₀ are each independently a single bond or a C1 to C10 alkylene group, R ₉ is a C1 to C10 alkylene group or -SiR ₁₁ R ₁₂ -, R ₁₁ and R ₁₂ are each independently a C1 to C10 alkylene group , and X is halo.

(12) In any one of (7) to (11) above, the present invention proposes a method for producing a multi-block copolymer, wherein the catalyst composition further includes a compound represented by the following formula 9.

[Formula 9]

In the above equation 9,

R _a is each independently a halogen group, a C1 to C20 hydrocarbon group, or a halogen-substituted C1 to C20 hydrocarbon group, and

m is an integer of 2 or more.

(13) In any one of the above (7) to (12), the present invention proposes a method for producing a multi-block copolymer, wherein the anionic polymerization initiator comprises an allyl group-containing alkyllithium compound, wherein This allyl group is bonded to lithium.

(14) In any one of (7) to (13) above, the present invention proposes a method for producing a multi-block copolymer, wherein the alkyllithium compound is represented by the following formula 11.

[Formula 11]

In the above equation 11,

R ₁₃ is hydrogen or C1 to C20 hydrocarbon, and

Am is an amine compound represented by the following formula 12.

[Formula 12]

In the above equation 12,

R ₁₄ to R ₁₈ are each independently hydrogen or C1 to C20 hydrocarbon, and

a and b are each independently an integer of 0 to 3, wherein a and b are not 0 at the same time. Efficacy of inventions compared to prior art

The multi-block copolymer proposed by the present invention has excellent mechanical properties (eg, tensile strength, elongation, and modulus), and thus can be usefully used in various industrial applications.

Hereinafter, the present invention will be described in more detail to facilitate understanding of the present invention.

It will be understood that the words and terms used in the description of the present invention and claims should not be limited to the meanings defined in commonly used dictionaries. It will be further understood that the words and terms should be interpreted on the basis that the inventor can properly define the words or terms to best explain the present invention, so as to have a meaning consistent with the context of the related art and the technical idea of the present invention.

In this specification, the term "alkyl" refers to a linear or branched hydrocarbon moiety.

In the present specification, the term "cycloalkyl" refers to a cyclic hydrocarbon moiety, and the cyclic hydrocarbon includes cyclic hydrocarbons in which two or more cyclic hydrocarbons are condensed, such as bicyclic hydrocarbons and tricyclic hydrocarbons.

In the present specification, the term "alkenyl" refers to straight-chain or branched-chain alkenyl.

In this specification, "aryl" is preferably C6 to C20, and may specifically be phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisole, etc., but is not limited thereto.

In the present specification, the term "alkaryl" refers to an aryl group substituted with the above alkyl group.

In the present specification, the term "aralkyl" refers to an alkyl group substituted with the above aryl group.

In this specification, the term "alkylsilyl" may be a silyl group substituted by C1 to C20 alkyl, for example, trimethylsilyl or triethylsilyl.

In the present specification, the term "alkylamino group" refers to an amino group substituted by the above alkyl group, and examples thereof include dimethylamino group, diethylamino group, etc., but the present invention is not limited to the above examples.

In this specification, unless otherwise stated, "hydrocarbon group" refers to a C1 to C20 monovalent hydrocarbon group composed only of carbon and hydrogen, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, Alkaryl or aralkyl.

In the present specification, the term "composition" includes not only reaction products and decomposition products formed from materials of the corresponding composition, but also mixtures of materials including the corresponding composition.

In this specification, the term "polymer" refers to a polymer compound obtained by polymerizing monomers (whether the same or different types). Thus, the generic term "polymer" encompasses both the term "homopolymer" (generally referring to a polymer made from only one monomer) and the term "interpolymer" as defined below.

In this specification, the term "copolymer" means a polymer obtained by polymerizing at least two different monomers.

In this specification, the number 0 after the decimal point "." may be omitted.

Hereinafter, the present invention will be described in detail.

multi-block copolymer

The multi-block copolymer of the present invention is a polyolefin-polystyrene-based multi-block copolymer comprising polystyrene-based blocks comprising repeating units derived from aromatic vinyl-based monomers and comprising polystyrene-based blocks derived from ethylene Repeating units and polyolefin-based blocks of repeating units derived from α-olefin-based monomers, wherein the polystyrene homopolymer measured by gel permeation chromatography (GPC) expressed by the following equation 1 is relative to a fraction of the polystyrene-based block of 4% or less; and a weight average molecular weight (MW) as measured by gel permeation chromatography (GPC) of 100,000 to 300,000 g/mol.

[equation 1] Homopolymer fraction (area%)=area of homopolystyrene peak∕(area of polystyrene block peak+area of homopolystyrene peak)×100(%)

The multi-block copolymer of the present invention is prepared by using a specific transition metal compound with a novel structure described below as a catalyst, and has a high weight average molecular weight, which is an important factor determining the physical properties of the copolymer , have a low content of homopolystyrene and have excellent tensile properties (eg, tensile strength, elongation, modulus, etc.) and excellent clarity, even with relatively few polyhydrocarbon branches.

In the multi-block copolymer of the present invention, the fraction of polystyrene homopolymer relative to the polystyrene-based block measured by gel permeation chromatography (GPC) is 4% or less, and specifically In other words, it can be 0.10% or more, 0.50% or more, 0.60% to 4%, 3.80% or less, 3.00% or less, 2.50% or less, 2.20% or less, 2.00% or lower, 1.90% or lower, or 1.80% or lower, and more specifically, may be 0.60% to 4%. The ratio of the polystyrene homopolymer to the polystyrene-based block can be obtained from the area ratio of the peaks in the chromatogram obtained by gel permeation chromatography, and specifically refers to the homopolystyrene The ratio of the peak area to the total peak area represented by the styrenic polymer. The fraction of the polystyrene homopolymer relative to the polystyrenic block can be represented by Equation 1 below.

[equation 1] Homopolymer fraction (area%)=area of homopolystyrene peak∕(area of polystyrene block peak+area of homopolystyrene peak)×100(%)

The smaller the fraction of polystyrene homopolymer contained in the multi-block copolymer of the present invention, the higher the transparency of the multi-block copolymer. Therefore, when the polystyrene homopolymer meets the fraction range relative to the polystyrenic block, the multi-block copolymer can have high transparency.

The multi-block copolymer has a weight average molecular weight (MW) of 100,000 g/mol to 300,000 g/mol, and specifically, may be 105,000 g/mol or higher, 300,000 g/mol or lower, or 250,000 g/mol mol or less, and more specifically, may be 120,000 g/mol to 200,000 g/mol.

The molecular weight distribution (PDI) of the multi-block copolymer is 1.5 to 3.0, and specifically, may be 1.52 or higher, 1.55 or higher, 1.58 or higher, 1.60 to 2.5, 2.3 or lower, 2.1 or higher Low, or 2.0 or less, and more specifically, may be 1.60 to 2.00.

The molecular weight distribution is calculated from the ratio of (weight average molecular weight)/(number average molecular weight), and the weight average molecular weight and number average molecular weight are polystyrene converted molecular weights analyzed by gel permeation chromatography (GPC).

The multi-block copolymers of the present invention conform to both the fraction of polystyrene homopolymer and the weight average molecular weight (MW) within the above ranges, and may additionally conform to the weight average molecular weight (PDI).

The polyolefin-polystyrene multi-block copolymer of the present invention comprises polystyrene blocks comprising repeating units derived from aromatic vinyl monomers and comprising repeating units derived from ethylene and derived from alpha-olefins is a polyolefin-based block of repeating units of monomers, wherein the polyolefin-polystyrene multi-block copolymer must include branched chains (wherein the polyolefin block of the multi-block copolymer is derived from the main chain), but The branching included is higher than that of typical polyolefin-polystyrene block copolymers (specifically, styrene-ethylene-butylene-styrene prepared by a typical two-step process of anionic polymerization and hydrogenation) Copolymers (SEBS) and styrene-ethylene-propylene-styrene copolymers (SEPS)) come in rare while exhibiting excellent physical properties.

The multi-block copolymer of the present invention is a polyolefin-polystyrene multi-block copolymer comprising polystyrene blocks comprising repeating units derived from aromatic vinyl monomers, and comprising polystyrene blocks derived from ethylene Repeating units and polyolefin blocks derived from repeating units of α-olefin monomers, wherein the α-olefin monomers can be C6 or higher carbon α-olefins, specifically, C8 or higher carbon α-olefins, or C8 to C20 α-olefins, and more specifically, C8 to C14 α-olefins.

In one example of the present invention, examples of the α-olefins may include 1-hexene, 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-octene.

The multi-block copolymer of the present invention can specifically be polystyrene-poly(ethylene-co-1-hexene)-polystyrene block copolymer or polystyrene-poly(ethylene-co-1-octene )-polystyrene block copolymer, and more specifically, may be a polystyrene-poly(ethylene-co-1-octene)-polystyrene block copolymer. As mentioned above, in the multi-block copolymer of the present invention, the polyolefin-based block may include branched chains derived from α-olefins with C6 or more carbons, specifically branched chains derived from α-olefins with C8 or more carbons. Branched chains, e.g., 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Eicosene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, or 3,4-dimethyl-1-hexene, specifically, 1- Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4,4-dimethyl -1-pentene, 4,4-diethyl-1-hexene, or 3,4-dimethyl-1-hexene, more specifically, 1-octene, and accordingly, the branched The length is long so that excellent physical properties are exhibited even with a relatively small number of branches.

By ¹ H NMR (500 MHz, tetrachloroethane-d2, standard TMS) spectrum measurement, the content of the repeating unit derived from the α-olefin monomer of the multi-block copolymer of the present invention can be 10mol% to 20 mol%, and specifically, the content of the repeating unit derived from α-olefin-based monomers may be 10.5 mol% or higher, 11 mol% or higher, 12 mol% to 19 mol%, 18.5 mol% or lower, 18 mol% or less, 17.5 mol% or less, or 17 mol% or less, and more specifically, may be 12 mol% to 17 mol%.

In addition, by ¹ H NMR (500 MHz, tetrachloroethane-d2, standard TMS) spectrum measurement, the content of repeating units derived from α-olefin monomers in the multi-block copolymer of the present invention can be 20 mol % to 40 mol%, and specifically, the content of repeating units derived from α-olefin-based monomers may be 21% by weight or higher, 21.5% by weight or higher, 22% by weight or higher, 22.5% by weight or Higher, 23% to 39% by weight, 38.5% by weight or less, or 38% by weight or less, and more specifically, may be 23% to 38% by weight.

When the content of the repeating unit derived from the α-olefin monomer meets the above mol% and weight% ranges, the multi-block copolymer can exhibit more excellent elongation and tensile strength.

In an 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 by C6 to C20 aryl, ethylene substituted by phenyl, etc., specifically phenethyl, α-methylbenzene Ethylene, vinyltoluene, C _1-3 alkyl substituted alkylstyrenes (e.g. o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene. .etc.) or halogen substituted styrene, and more specifically styrene.

By ¹ H NMR (500 MHz, tetrachloroethane-d2, standard TMS) spectrum measurement, the content of repeating units derived from aromatic vinyl monomers in the multi-block copolymer of the present invention can be 5 mol% to 20 mol%, and specifically, the content of the repeating unit derived from an aromatic vinyl monomer may be 6 mol% or higher, 6.5 mol% or higher, 7 mol% or higher, 7.5 mol% or more High, 8mol% or higher, 8.1mol% or higher, 8.2mol% to 19mol%, 18mol% or lower, 17mol%, 16.5mol% or lower, 16mol% or lower, 15.8mol% or lower , or 15.5 mol% or less, and more specifically, 8.2 mol% to 15.8 mol%.

In addition, by ¹ H NMR (500 MHz, tetrachloroethane-d2, standard TMS) spectrum measurement, the content of the repeating unit derived from the aromatic vinyl monomer of the multi-block copolymer of the present invention can be 15 mol% to 35 mol%, and specifically, the content of the repeating unit derived from an aromatic vinyl monomer may be 16% by weight or higher, 16.5% by weight or higher, 17% by weight or higher, 17.5 % by weight or higher, 18% by weight to 34% by weight, 33.5% by weight or lower, 33% by weight or lower, 32.5% by weight or lower, 32% by weight or lower, or 31% by weight or lower, And more specifically, it may be 18% by weight to 32% by weight.

When the content of the repeating unit derived from the aromatic vinyl monomer meets the above mol% range and weight% range, the multi-block copolymer can exhibit more excellent transparency.

Method for the preparation of multi-block copolymers

The preparation method of the multi-block copolymer of the present invention includes (S1) using an organozinc compound as a chain transfer agent, in the presence of a catalyst composition including a transition metal compound, by reacting ethylene and an α-olefin monomer to prepare a polymer Olefin-based block; and (S2) In the presence of alkyllithium compound and amine-based compound, the multi-block copolymer is produced by reacting aromatic vinyl monomer and polyolefin-based block.

Step (S1)

The step (S1) is a step of preparing a polyolefin block by reacting ethylene and an α-olefin monomer by using an organic zinc as a chain transfer agent in the presence of a catalyst composition including a transition metal compound.

According to an embodiment of the present invention, the transition metal compound is a catalyst for growing olefin-based polymers through coordination chain transfer polymerization, and may be a catalyst including a main catalyst (which is a transition metal) and an auxiliary catalyst. media composition.

In the present invention, the transition metal compound is a compound represented by the following formula 1.

[Formula 1]

In the above formula 1,

M is Ti, Zr, or Hf,

R ₁ to R ₄ 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 aromatic group, wherein two or more adjacent ones can be connected to each other and form a ring,

R ₅ and R ₆ 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 aromatic group, wherein the substitution is carried out with a C1 to C12 alkyl group,

_Each R is independently substituted or unsubstituted C4 to C20 alkyl, substituted or unsubstituted C4 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl, and

n is 1 to 5, and

Y and Y _are each independently halo, 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 alkaryl, 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 base.

Specifically, in Formula 1 above, M may be Hf.

In addition, specifically, in the above formula 1, _R1 to _R4 may each independently be hydrogen, or a substituted or unsubstituted C1 to C20 alkyl group, wherein two or more adjacent ones may be connected to each other and form a ring. Alternatively, R ₁ to R ₂ are each independently a C 1 to C 20 alkyl group, which are connected to each other and form a C 5 to C 20 aromatic ring, and R ₃ and R ₄ may be hydrogen.

In addition, specifically, in the above formula 1, R ₅ and R ₆ may each independently be hydrogen, or a substituted or unsubstituted C6 to C20 aryl group, wherein the substitution may be performed with a C1 to C6 alkyl group.

In addition, specifically, in the above formula 1, R ₇ can each independently be a substituted or unsubstituted C4 to C20 alkyl, a substituted or unsubstituted C4 to C20 cycloalkyl, or a substituted or unsubstituted Substituted C6 to C20 aryl.

Specifically, in the above formula 1, n may be 1 to 3, preferably 2.

Specifically, in Formula 1 above, Y ₁ and Y ₂ may each independently be a C1 to C20 alkyl group.

More specifically, the transition metal compound represented by Formula 1 above may be a compound represented by Formula 1a below.

[Formula 1a]

In the above formula 1a,

M, R ₅ to R ₇ , and Y ₁ and Y ₂ are the same as defined above.

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 the present invention.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

In addition, the present invention provides a ligand compound represented by the following formula 2.

[Formula 2]

In the above formula 2,

R ₁ to R ₄ are each independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl, wherein two or more neighbors may be connected to each other and form a ring,

R ₅ and R ₆ 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 aromatic group, wherein the substitution is carried out with a C1 to C12 alkyl group,

_Each R is independently substituted or unsubstituted C4 to C20 alkyl, substituted or unsubstituted C4 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl, and

n is 1 to 5.

That is, the transition metal compound of the present invention can be produced by including a step of reacting a ligand compound represented by Formula 2 below and a compound represented by Formula 3 below.

[Formula 2]

[Formula 3]

In the above formula,

R ₁ to R ₇ , M, and Y ₁ and Y ₂ are the same as defined above.

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.

[Reaction 1]

[Reaction 2]

In the present invention, the organozinc compound is used as a chain transfer agent to induce chain transfer during the preparation of the copolymer in the polymerization reaction, wherein the chain transfer agent can be prepared by coordination chain transfer polymerization Chain transfer agent for copolymers.

In one example of the present invention, the chain transfer agent may include an organozinc compound represented by the following formula 5, and specifically, the chain transfer agent may include 96 mol% or more of the organozinc compound represented by the following formula 5, And preferably, the chain transfer agent does not include any side reaction products except the organozinc compound represented by the following formula 5.

[Formula 5]

In the above formula 5,

R ₈ and R ₁₀ may each independently be a single bond or C1 to C10 alkylene, R ₉ may be C1 to C10 alkylene or -SiR ₁₁ R ₁₂ -, and R ₁₁ and R ₁₂ may each independently be C1 to C10 alkyl.

In addition, according to an embodiment of the present invention, in the above formula 5, R ₈ and R ₁₀ can each independently be a single bond or a C1 to C10 alkylene group, and R ₉ can be a C1 to C10 alkylene group or -SiR ₁₁ R ₁₂ -, and R ₁₁ and R ₁₂ can each independently be C1 to C10 alkyl.

According to an embodiment of the present invention, the organozinc compound represented by the above formula 5 may be selected from the group consisting of the organozinc compounds represented by the formulas 5-1 to 5-4, and is preferably of the formula Either 5-3 or 5-4.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

According to an embodiment of the present invention, the chain transfer agent may include 97 mol% or more of the organic zinc compound represented by the above formula 5, more preferably 98 mol% or higher, or 99 mol% or higher, and most preferably , except for the organozinc compound, excluding any side reaction products. This means that the chain transfer agent does not include any side reaction products (eg, dimer) and impurities containing chlorine or magnesium, except for the organozinc compound represented by formula 5. That is, the chain transfer agent may include only the organozinc compound represented by Formula 5 above.

When ethylene and the α-olefin monomer system use the organic zinc compound represented by the above formula 5 as a chain transfer agent, when the ethylene and the α-olefin monomer react in the presence of a catalyst composition including a transition metal compound Interposed between zinc (Zn) and R ₁₀ of the organozinc compound, polymerization can be performed. In an example of the production method of the multi-block copolymer of the present invention, when the compound of the above formula 4 is used as the organozinc compound to prepare a polyolefin block by reacting ethylene and an α-olefin monomer, an olefin It is a polymer block intermediate product, and an example of the olefin-based polymer block intermediate product can be represented by the following formula 6.

[Formula 6]

In the above formula 6, R ₈ and R ₁₀ can each independently be a single bond or a C1 to C10 alkylene group, R ₉ can be a C1 to C10 alkylene group or -SiR ₁₁ R ₁₂ -, R ₁₁ and R ₁₂ can each be are independently C1 to C10 alkyl, and PO can be an olefinic polymer block.

According to an embodiment of the present invention, the organic zinc compound represented by the above formula 5 can be prepared by including the steps of preparing a Grignard reagent containing a styrene moiety, and reacting the prepared Grignard reagent with a zinc compound The organozinc compound is obtained by the preparation method, and the organozinc compound can be an alkyl zinc alkoxide.

According to an embodiment of the present invention, the organozinc compound represented by the above formula 5 prepared according to the preparation method of the organozinc compound is synthesized as a single compound, and therefore does not include any side reaction products (such as dimers), and in addition, does not Including impurities containing chlorine, which are catalyst poisons, such as organic zinc chloride (R-Zn-Cl)). In addition, when the organozinc compound represented by the above formula 5 is produced according to the production method of the organozinc compound, the organozinc compound is synthesized as a single compound, so there is an effect of excellent synthesis reproducibility. Meanwhile, when preparing organic zinc compounds, in order not to include side reaction products and impurities as in the present invention, it is important to select Grignard reagents and zinc compounds containing styrene moieties.

According to an embodiment of the present invention, the Grignard reagent containing a styrene moiety can be represented by the following formula 7.

[Formula 7]

In the above formula 7, R ₈ and R ₁₀ may each independently be a single bond or a C1 to C10 alkylene group, R ₉ may be a C1 to C10 alkylene group or -SiR ₁₁ R ₁₂ -, R ₁₁ and R ₁₂ may be Each is independently a C1 to C10 alkyl group, and X may be a halo group.

In addition, according to an embodiment of the present invention, in the above formula 7, R ₈ and R ₁₀ can each independently be a single bond or a C1 to C10 alkylene group, and R ₉ can be a C1 to C10 alkylene group or -SiR ₁₁ R ₁₂ -, and R ₁₁ and R ₁₂ may each independently be a C1 to C10 alkyl group.

According to an embodiment of the present invention, the Grignard reagent containing a styrene moiety and represented by the above formula 7 may be composed of a Grignard reagent containing a styrene moiety selected from each of the following formulas 7-1 to 7-4. one of the groups.

[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

[Formula 7-4]

According to an embodiment of the present invention, the Grignard reagent containing a styrene moiety and represented by the above formula 7 can be obtained via a halide (wherein the halide (-X) replaces R ₈ ) and magnesium (specifically, magnesium powder or magnesium metal ) The reaction between prepared.

According to an embodiment of the present invention, the Grignard reagent containing a styrene moiety and represented by the above formula 7 can be prepared by reacting a compound represented by the following formula 8 and magnesium (specifically, magnesium powder or magnesium metal) .

[Formula 8]

In the above formula 8, R ₈ and R ₁₀ can each independently be a single bond or a C1 to C10 alkylene group, R ₉ can be a C1 to C10 alkylene group or -SiR ₁₁ R ₁₂ -, R ₁₁ and R ₁₂ can each be are independently C1 to C10 alkyl, and X may be halo.

According to an embodiment of the present invention, in the above formula 8, R ₈ and R ₁₀ can each independently be a single bond or a C1 to C3 alkylene group, and R ₉ can be a C1 to C3 alkylene group or -SiR ₁₁ R ₁₂ -, R ₁₁ and R ₁₂ may each independently be a C1 to C3 alkyl group, and X may be a halo group.

In addition, according to an embodiment of the present invention, in the above formula 8, R ₈ and R ₁₀ can each independently be a single bond or a C1 alkylene group, R ₉ can be a C1 alkylene group or -SiR ₁₁ R ₁₂ -, R ₁₁ and R ₁₂ may each independently be C1 alkyl, and X may be a halo selected from the group consisting of Cl, Br, and I.

According to an embodiment of the present invention, the compound represented by the above formula 8 may be one selected from the group consisting of compounds represented by the following formulas 8-1 to 8-4.

[Formula 8-1]

[Formula 8-2]

[Formula 8-3]

[Formula 8-4]

According to an embodiment of the present invention, when preparing the Grignard reagent containing a styrene moiety and represented by the above formula 7, the reaction between the compound represented by the above formula 8 and magnesium powder or magnesium metal can be based on the molar percentage, With respect to 1 mol of the compound represented by the above formula 8, the mole percentage of magnesium powder or magnesium metal is excessive, that is, carried out under the situation that the mole percentage is greater than 1 mole, and here, 50 mol% or more High, 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, the compound represented by the above formula 8 can be converted into Grignard reagents containing styrene moieties.

According to an embodiment of the present invention, the reaction between the compound represented by the above formula 8 and magnesium powder or magnesium metal can be based on the 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, and within this range, the conversion rate of the Grignard reagent containing the styrene moiety and represented by the above formula 7 is high, Simultaneously, the residual magnesium content after the reaction is reduced to the minimum to facilitate the removal of residual magnesium powder or magnesium metal.

According to an embodiment of the present invention, when preparing an organic zinc compound, the zinc compound must be a zinc compound capable of inducing zinc to replace two organic groups of the same type based on zinc. Thus, zinc chloride (ZnCl ₂ ) is easily taken into consideration, but when zinc chloride is used as the zinc compound, impurities containing chlorine (which can become catalyst poisons) are left behind (e.g., alkylzinc chlorides) The problem. Therefore, in the present invention, an alkylzinc alkoxide is used as the zinc compound.

According to an embodiment of the present invention, the alkyl group of the alkylzinc alkoxide can be a C1 to C10 alkyl group, a C1 to C5 alkyl group, a C1 to C3 alkyl group, or an ethyl group, and the alkoxy group can be a C1 to C10 alkyl group. C10 alkoxy, C1 to C5 alkoxy, C1 to C3 alkoxy, or methoxy. As a specific example, the zinc compound may be ethyl zinc methoxide.

According to an embodiment of the present invention, the alkylzinc alkoxide can be prepared from dialkylzinc. As a specific example, the alkylzinc alkoxide can be prepared by in-situ reaction of dialkylzinc with alcohol. At this time, the alkyl group of the dialkylzinc may be the same as that of the above alkylzinc alkoxide, and the alcohol may be an alcohol whose hydrogen is bonded to the alkoxy group of the above alkylzinc alkoxide.

According to an embodiment of the present invention, when the alkylzinc alkoxide is used as the zinc compound, during the reaction between the Grignard reagent and the zinc compound, a magnesium halide alkoxide is formed, which is an insoluble salt that is easy to filter, It is thus possible to prevent impurities from remaining.

According to an embodiment of the present invention, based on the molar ratio, the reaction between the Grignard reagent and the zinc compound can be 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 a molar ratio of 1:1, and within this range, the organozinc compound is synthesized as a single compound, and therefore does not include any side reaction products, such as , dimer, and does not include impurities containing chlorine (which can be used as a catalyst poison), and has the effect of easily removing impurities containing magnesium (which can be used as a catalyst poison).

According to the embodiments of the present invention, all steps and all reactions of the zinc compound preparation method can be carried out in an organic solvent, and the reaction temperature and reaction pressure can be adjusted according to the purpose of improving yield and purity.

According to the preparation method of the zinc compound of the embodiment of the present invention, the Grignard reagent containing the styrene moiety is used to replace the borane compound containing the typical styrene moiety, and the alkyl zinc alkoxide is used to replace the alkyl zinc or zinc chloride, The catalyst poison can thus be completely removed.

In addition, by modifying the above method, unlike the prior art that obtains a mixture of dimers, trimers, and zinc compounds with saturated endpoints as products, a single compound can be obtained in the form of a monomer with fully preserved vinyl endpoints Therefore, it not only improves the storage stability of the zinc compound, but also improves the physical properties of the final compound, and can achieve the effect of greatly reducing the yield of the diblock copolymer compared with the triblock copolymer.

In addition, the catalyst composition may further include a compound represented by the following formula 9, and the compound represented by the above formula 8 may serve as an auxiliary catalyst, a scavenger, or both.

[Formula 9]

In the above formula 9,

Each R _a is independently halo, a hydrocarbyl of 1 to 20 carbon atoms, or a halogen substituted hydrocarbyl of 1 to 20 carbon atoms, and

m is an integer of 2 or more.

There is no particular limitation on the compound represented by the above formula 9 as long as it is an alkylaluminoxane. Preferred examples include modified methylaluminoxane (MMAO), methylaluminoxane (methylaluminoxane MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., And a particularly preferred compound may be modified methylalumoxane (MMAO).

The compound represented by the above formula 9 is a compound in the form of an oligomer produced by the reaction of an aluminum alkyl and water, and when the compound is used as a cocatalyst, the chain transfer is reduced. Therefore, a high-molecular-weight copolymer can be produced, and the generation of homopolyolefin as a side reaction can also be prevented. Therefore, finally, a polyolefin-polystyrene multi-block copolymer exhibiting excellent physical properties such as high tensile strength can be obtained.

Meanwhile, while the above chain transfer can be suppressed by the compound represented by the above formula 9, if the compound (e.g., alkylaluminum) is used as an auxiliary catalyst, a large amount of chain transfer occurs, so that the molecular weight of the copolymer is lowered and the homopolyolefin The increase in the generation of , which causes the problem of deterioration of the physical properties of the block copolymer.

As mentioned above, in the present invention, the transition metal compound represented by formula 1 and the compound represented by formula 9 are used in combination to obtain a multi-block copolymer meeting the aforementioned conditions.

In addition, the transition metal compound represented by the above formula 1 and the compound represented by the above formula 9 may also be used in a supported form. Silica and alumina can be used as the support, but the support is not limited thereto.

In addition, the catalyst composition may further include a compound represented by Formula 10 below.

[Formula 10]

In the above formula 10,

Z is a group 13 element,

A is each independently a C6 to C20 aryl group, wherein one or more hydrogen atoms may be substituted by a substituent, or a C1 to C20 alkyl group, and

The substituent of A is halogen, C1 to C20 hydrocarbon group, C1 to C20 alkoxy group, or C6 to C20 aryloxy group.

Step (S1) can be performed, for example, in a homogeneous solution state. At this time, as a solvent, a hydrocarbon solvent or an olefin-based monomer itself can be used as a medium. The hydrocarbon solvent may be a C4 to C20 aliphatic hydrocarbon solvent, specifically isobutane, hexane, cyclohexane, methylcyclohexane, and the like. These solvents may be used alone, or two or more of them may be used in combination.

The polymerization reaction temperature of step (S1) may vary depending on reactants, reaction conditions, etc., but may be specifically 70 to 170°C, specifically 80 to 150°C, or 90 to 120°C. Within the above range, the solubility of the polymer can be increased and the catalyst can be thermally stabilized.

The polymerization reaction of 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.

The compound prepared by the above step (S1) can be used as a precursor for preparing the polyolefin-polystyrene multi-block copolymer of the present invention by the anionic polymerization reaction of the step (S2) described later.

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

In an example of the present invention, the α-olefin can be one or more selected from 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-deca Tetracene, 1-hexadecene, 1-eicosene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, and 3,4-di Methyl-1-hexene, and more specifically, may be 1-hexene.

Step (S2)

The step (S2) is a step of preparing the multi-block copolymer by reacting the aromatic vinyl monomer and the polyolefin block in the presence of an anionic polymerization initiator.

In the step (S2), the aromatic vinyl-based monomer is continuously inserted between the zinc-carbon bonds of (polyolefin group) ₂ Zn contained in the compound formed by the above-mentioned step (S1), thereby forming polyphenylene Vinyl tether, and at the same time, the styryl group derived from the chain extender present at the end of the compound formed by step (S1) can participate as a The copolymerization reaction point. In addition, the multi-block copolymers prepared through the above procedures are easily cleaved by the reaction of terminal groups with water, oxygen, or organic acids, whereby the multi-block copolymers are converted into industrially useful polyolefin-polymer Styrenic multi-block copolymer.

The aromatic vinyl monomer may be a C6 to C20 aromatic vinyl monomer. For example, the aromatic vinyl-based monomer may be an aromatic vinyl-based monomer including C6 to C20 aryl-substituted ethylene, phenyl-substituted ethylene, etc., specifically styrene, α-methylstyrene , vinyl toluene, alkyl styrenes substituted by C _1-3 alkyl groups (such as o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, etc.) Or halogen substituted styrene, and more specifically styrene.

In one example of the present invention, the anionic polymerization initiator may be an alkyllithium compound represented by Formula 11 below.

[Formula 11]

In the above equation 11,

R ₁₃ is hydrogen or C1 to C20 hydrocarbon, and

Am is an amine compound represented by the following formula 12.

[Formula 12]

In the above equation 12,

R ₁₄ to R ₁₈ are each independently hydrogen or C1 to C20 hydrocarbon, and

a and b are each independently an integer of 0 to 3, wherein a and b are not 0 at the same time.

In one example of the present invention, R ₁₃ can be hydrogen, C1 to C20 alkyl, C3 to C20 cycloalkyl, or substituted or unsubstituted C7 to C20 aralkyl,

R ₁₄ to R ₁₈ can each independently be hydrogen, C1 to C20 alkyl, C1 to C20 alkenyl, C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted substituted C7 to C20 aralkyl, and

a and b may be an integer of 0 to 2 each independently.

In addition, in an example of the present invention, R ₁₃ to R ₁₈ can each independently be hydrogen or C1 to C20 alkyl, wherein a can be 1 or 2, and b can be 0 or 1.

Specifically, a can be an integer of 1 to 3, and b can be an integer of 0 to 3, and more specifically, a can be 1 or 2, and b can be an integer of 0 to 2, and more specifically , a can be 1 or 2, and b can be 0 or 1.

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

[Formula 13]

[Formula 14]

In the above formula,

R ₁₄ , R ₁₅ , and R ₁₈ are each independently hydrogen or C1 to C20 alkyl.

In addition, in an example of the present invention, in the above formula 11, Am can be specifically represented by the following formula 13a or formula 14a.

[Formula 13a]

[Formula 14a]

In the preparation method of the multi-block copolymer of the present invention, the compound represented by the above formula 11 is used as an anionic polymerization initiator, therefore, the polyolefin tether that can be obtained from step S1 has been prepared in an organozinc compound (especially is a polyolefin-grown polystyrene tether of (polyolefin-based) _2Zn grown near zinc (Zn). As mentioned above, in the production method of the multi-block copolymer of the present invention, polystyrene-polyolefin-polystyrene multi-block can be obtained by growing polystyrene tethers at both ends of the polyolefin chain Copolymers, therefore, the resulting multi-block copolymers can have a nearly symmetrical structure and can have consistent polystyrene block sizes.

This anionic polymerization initiator can be obtained by the following method.

The method of preparing the anionic polymerization initiator includes a procedure of introducing a compound represented by the following formula 16 and a compound represented by the formula 12 in the presence of the compound represented by the following formula 15 to react.

[Formula 12]

[Formula 15]

[Formula 16]

In the above formula,

R ₁₃ to R ₁₈ are each independently hydrogen or C1 to C20 hydrocarbon,

a and b are each independently an integer from 0 to 3, wherein a and b are not 0 at the same time, and

B is C1 to C20 alkyl.

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

In addition, in an example of the present invention, R ₁₄ to R ₁₈ may each independently be 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.

Specifically, a may be an integer of 1 to 3, and b may be an integer of 0 to 3, and more specifically, a may be 1 or 2, and b may be an integer of 0 to 2, and more specifically, a can be 1 or 2, and b can be 0 or 1.

The alkyllithium compound represented by the above formula 16 may be, for example, n-BuLi, wherein n-BuLi is a material widely used as an initiator of anionic polymerization reaction, and is readily available and has excellent unit cost-effectiveness.

In the preparation method of this anionic polymerization initiator, the procedure of reacting the compound represented by the above formula 16 with the compound represented by the above formula 15 can be carried out first, and then the compound of the formula 12 can be reacted with it to obtain the compound of the above formula 11 . Specifically, the compound represented by the above formula 16 is reacted with the compound represented by the above formula 15 to produce an allyllithium intermediate product, and the allyllithium is reacted with the compound of the formula 12 to finally form the anion of the above formula 11 A polymerization initiator.

In addition, the procedure of reacting by introducing the compound represented by the above formula 16 and the compound represented by the above formula 12 in the presence of the compound represented by the above formula 15 can be performed without an additional solvent. The condition of no additional solvent means that, in the presence of the compound represented by the above formula 16, no other compound is used as a solvent other than the compound represented by the above formula 15 and the compound represented by the above formula 12, or means, Additional solvent was present in minor amounts and thus did not significantly react with compounds of formula 15 above.

When the reaction is carried out without an additional solvent, the reaction of the compound represented by the above formula 15 and the compound represented by the above formula 16 is carried out as the main reaction, so the anionic polymerization initiator of the formula 11 can be efficiently produced . When there is no additional solvent, the anionic polymerization initiator of the above formula 11, the compound obtained by reacting the compound represented by the above formula 15 with the compound represented by the above formula 12, and the compound obtained by reacting the compound represented by the above formula 15 with The compounds produced by the reaction of the compounds represented by the above formula 12 and the compounds decomposed are all mixed and present, and thus are inefficient.

example

Hereinafter, the present invention will be described in detail with reference to examples. But the following examples only illustrate the present invention and are not intended to limit the scope of the present invention.

Reagents and Experimental Conditions

All experiments were performed under inert gas using a standard glove box and using the Schlenk technique. Toluene, hexane, and tetrahydrofuran (THF) were distilled with benzophenone and used. Methylcyclohexane (anhydrous grade) used for the polymerization was purchased from Tokyo Chemical Industry (TCI) and purified with Na/K alloy and used. Sublimation grade HfCl ₄ was purchased from Streme and used as received. The ethylene-propylene gas mixture was purified in a bomb reactor (2.0 L) with trioctylaluminum (0.6 M, in mineral systems) and used.

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

GPC data were obtained 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]) in 1,2,4-trichlorobenzene at 160 ℃ analysis.

Preparation example

(1) Preparation of transition metal compounds

[Formula 1-1]

(i) Preparation of ligand compounds

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) and molecular sieves were added thereto. The mixture was heated to 70°C overnight with stirring. After filtration, the solvent was removed from a rotary evaporator. A yellow solid (1.07 g, 84%) was obtained.

¹ H NMR(C ₆ D 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.

¹³ C NMR (C ₆ D 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 .06 ppm.

HRMS (EI): _m /z calcd ([M ⁺ ] _C24H29BrN2 ) 424.1514 _. Experimental value: 424.1516.

A Schlenk bottle was charged with this compound (1.07 g, 2.51 mmol), 1-naphthylboronic acid (0.453 g, 2.64 mmol), Na ₂ CO ₃ (0.700 g, 6.60 mmol), and toluene (5 mL) under nitrogen. (Ph ₃ P) ₄ Pd (7.83 mg, 0.00678 mmol) solution was added to degassed H ₂ O/EtOH (1 mL, v/v , 1:1) and toluene (1 mL). A pale yellow oil (0.712 g, 60%) was obtained by column chromatography on silica gel using ethyl acetate with hexane and a small amount of triethylamine ( v/v , 90:3:1).

¹ H NMR(C ₆ D 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.

¹³ C NMR (C ₆ D 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.

_HRMS (EI): m/z calcd ([M ⁺ ] _C34H36N2 ) _472.2878 . Experimental value: 472.2878.

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) . After stirring for 3 hours, an aqueous solution (10 mL) of ammonium chloride (0.30 g) was added and the product was extracted with diethyl ether (3 x 10 mL). The resulting oil was dried overnight at 60°C under high vacuum. A yellow solid (0.257 g, 83%) was obtained.

¹ H NMR(C ₆ D 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.

¹³ C NMR (C ₆ D 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, 1 25.36, 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.

HRMS (EI): m/z calcd ([M ⁺ ] _C43H48N2 ) _{592.3817 .} Experimental value: 592.3819.

(ii) Preparation of transition metal compounds

A Schlenk bottle was charged with the ligand compound (0.150 g, 0.253 mmol) in toluene (1.5 g), and n-BuLi (0.17 mL, 1.6 M solution in toluene, 0.27 mmol) was added dropwise at room temperature. Stir for 1 hour, then add _HfCl4 (0.0814 g, 0.254 mmol) as a solid. 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 thereto and stirred at room temperature overnight. After removal of volatiles with vacuum line, the product was extracted with toluene (1.5 g). The extract was obtained by filtration through a cellite. After removing the solvent via vacuum line, the residue was softened in hexane (2 mL) to give a yellow solid (0.128 g, 63%).

¹ H NMR(C ₆ D 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.

¹³ C NMR (C ₆ D 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.

analyze. Theoretical (C ₄₅ H ₅₂ HfN ₂ ): C, 67.61; H, 6.56; N, 3.50%. Calculated: C, 67.98; H, 6.88; N, 3.19%.

(2) Preparation of organozinc compounds

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 hour, then filtered on a Celite filter to remove Remove excess magnesium. 19.2 g (81.9 mmol) of p-toluenesulfonyl-OCH ₂ CH ₂ Cl were dissolved in 27 ml of diethyl ether, and added dropwise to the prepared 4-vinylbenzyl-magnesium chloride (4-vinylbenzyl base-MgCl) Grignard reagent. Stir overnight, then filter on a celite filter to remove magnesium tosylsulfonyl chloride (MgCl(OTs)), an insoluble salt. The filtered filter cake was washed three times with 70 ml of hexane, and the solvent was removed with a rotary evaporator to obtain 14.2 g of crude product. 43 mg (3,000 ppm) of tertiary butylcatechol was added as a group-removing agent, and vacuum distillation was performed at 85° C. under full vacuum to obtain a compound represented by the following formula 8-4-1. As a result of measuring the weight of the obtained compound, the obtained yield was 81% by weight, and ¹ H NMR and ¹³ C NMR spectra were measured.

[Formula 8-4-1]

¹ H NMR (C ₆ D 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 ₂ Cl) ppm.

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

After that, 10.0 g (55.3 mmol) of the obtained compound (4-(3-chloropropyl) styrene) represented by the above 8-4-1 was dissolved in 20 ml of toluene and 7.98 g (111 mmol) of Tetrahydrofuran (THF) in a mixed solvent, and added dropwise to a suspension of 2.02 g (83.0 mmol) of magnesium powder in 40 mL of toluene at room temperature. After stirring for 5.0 hours, with gradual warming, the reaction mixture was filtered on a celery filter to remove excess added magnesium. 6.94 g (55.3 mmol, 1 equivalent relative to Grignard reagent) of ethyl zinc methoxide (by making 6.83 g (55.3 mmol) of diethyl zinc (Et ₂ Zn) and 1.78 g (55.3 mmol) of Methanol (prepared in situ at room temperature for 1.0 hour in 30 ml of toluene) was added to the filtrate. Then, 60 ml of toluene was added thereto, followed by stirring at room temperature for 1.0 hour, and then the solvent was removed using a high vacuum line. Afterwards, 96 g of hexane was added thereto, and magnesium chloride methoxide (MgCl(OMe)), an insoluble salt, was removed on a celery filter. The filtrate was stored at -30°C so that the compound represented by Formula 5-4 was deposited as a white crystalline solid. As a result of weight measurement, the obtained yield was 56% by weight (7.28 g), and ¹ H NMR and ¹³ C NMR were measured.

[Formula 5-4]

¹ H NMR (C ₆ D 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 ₂ Zn) ppm.

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

(3) Preparation of anionic polymerization initiator

n-BuLi (0.14 mg, 2.2 mmol) was added dropwise to pentamethyldiethylenetriamine (PMDTA, 0.37 g, 2.2 mmol) in 1-octene (13.0 g). After stirring overnight at room temperature, a yellow solution of pentylallyl-Li·(PMDTA) (0.16 mmol-Li/g) was obtained. A portion was analyzed by ¹ H NMR spectroscopy. ¹ H NMR spectra were recorded, and the C ₆ D ₆ solution was stripped of H ₂ O (or D ₂ O) and filtered in a pipette with a short pad of anhydrous MgSO ₄ to record ^{the 1} H NMR spectra again.

polyolefin - Preparation of polystyrene-based multi-block copolymers

example 1

A Parr reactor (3.785 L) was dried in vacuo at 120°C for 2 hours. As a scavenger, a solution of MMAO (0.6 mg, 1,000 μmol-Al) in methylcyclohexane (1,200 g) was introduced into the reactor, then using a heating mantle, the mixture was stirred at 120 °C for 1 hour, after which, Use a cannula to remove the solution.

The reactor was filled with methylcyclohexane (1,200 g) containing MMAO (1,000 μmol-Al) as a scavenger, and 1-hexene (560 g) as an α-olefin monomer, and then the temperature was set at 90 ℃. A solution of the organozinc compound (3,100 μmol) of the above formula 5-4 in methylcyclohexane (5 g) was filled as a chain transfer agent, and then injected with [(C ₁₈ H ₃₇ ) ₂ N(H)Me] + [B(C ₆ F ₅ ) ₄ ] ^- (1.0 eq) Methylcyclohexane solution of activated transition metal compound (12 μmol-Hf) in Methylcyclohexane. Polymerization was carried out in the range of 90 to 120° C. for 40 minutes while maintaining the pressure in the reactor at 25 bar by opening the valve of the ethylene tank. After polymerization, ethylene gas was vented and the temperature of the reactor was then adjusted back to 90°C.

When the temperature reached 90°C, pentylallyl-Li·(PMDTA) (1,600 μmol) in methylcyclohexane (10 g) was added. While stirring, the temperature was maintained at 90° C. for 30 minutes, then styrene (90 g) was injected. The temperature was adjusted in the range of 90 to 100°C using a heating mantle. Within 5 hours, the viscosity gradually increased and reached an almost invisible state. A portion was obtained for analysis by ¹ H NMR spectrometer. Complete conversion of styrene was confirmed by ¹ H NMR optical analysis of a portion. After complete conversion of styrene, 2-ethylhexanoic acid and ethanol were injected sequentially. The resulting polymer mass was dried overnight in a vacuum oven at 80°C.

example 2 to 8

A multi-block copolymer was prepared in the same manner as in Example 1, but the reaction conditions were changed as shown in Table 1 below.

example 9

A multi-block copolymer was prepared in the same manner as in Example 1, but 1-hexene was used instead of 1-octene as the α-olefin monomer in Example 1, and the reaction conditions were changed as shown in Table 1 below By.

comparative example 1

A multi-block copolymer was 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.

comparative example 2

Me ₃ SiCH ₂ Li (2,600 μmol, 291.4 mg) and PMDETA (2,600 μmol, 537.3 mg) were mixed with methylcyclohexane (20.7 g) and then injected into the reactor, followed by stirring for 30 minutes. The anionic polymerization initiator is prepared by maintaining the stirring temperature at 90°C to 100°C.

A multi-block copolymer was prepared in the same manner as in Example 1, but using the above-prepared Me ₃ SiCH ₂ Li (PMDETA) instead of pentylallyl-Li (PMDTA) as the anionic initiator in Example 1 agent, and the reaction conditions were changed to those shown in Table 1 below.

comparative example 3

Prepare multi-block copolymers in the same manner as in Example 1, but use Oc ₃ Al (1976.7 mg, 1,348 μmol-Al/25% by weight in hexane) instead of MMAO as the scavenger in Example 1, and the reaction conditions changed to those shown in Table 1 below.

comparative example 4

A multi-block copolymer was prepared in the same manner as in Example 1, but 1-hexene was used instead of 1-octene as the α-olefin monomer in Example 1, and the reaction conditions were changed as shown in Table 1 below By.

[Table 1]

Experimental example 1

The physical properties of the polyolefin-polystyrene multi-block copolymers of each of Examples and Comparative Examples were measured as follows.

(1) Measurement of ethylene, α-olefin, and styrene content

The measurement is performed via nuclear magnetic resonance (NMR). Using a Bruker 600MHz AVANCE III HD NMR device, ¹ H NMR was measured under the conditions of ns=16, d1=3s, solvent=TCE-d2, and 373K, and the TCE-d2 solvent peak was corrected to 6.0 ppm. The CH ₃ of 1-propene was confirmed at 1 ppm and the CH ₃ -related peak (triplet) of the butyl branch of 1-hexene was confirmed near 0.96 ppm to calculate the content. Additionally, the styrene content was calculated using the aromatic peak near 6.5 to 7.5 ppm.

(2) Weight average molecular weight (Mw, g/mol) and polydispersity index (PDI)

The weight average molecular weight (Mw, g/mol) and the number average molecular weight (Mn, g/mol) were measured by gel permeation chromatography (GPC), and the weight average molecular weight was divided by the number average molecular weight to calculate the polydispersity index (PDI).

- Column: PL Olexis

- Solvent: TCB (trichlorobenzene)

- Flow rate: 1.0 ml/min

- Sample concentration: 1.0 mg/ml

- Injection volume: 200㎕

- Column temperature: 160°C

- Detector: Agilent high temperature RI detector

- Standard: polystyrene

- Calculate the molecular weight using the Mark-Houwink equation (K = 40.8 × 10 ^-5 , α = 0.7057) with universal calibration

- Calculate the molecular weight using the Mark-Houwink equation (K = 40.8 × 10 ^-5 , α = 0.7057) with universal calibration

(3) Fraction of homopolystyrene

After measuring the multi-block copolymers of Examples and Comparative Examples using gel permeation chromatography (GPC) to obtain GPC chromatograms, according to the following Equation 1, the peak area shown by homopolystyrene is different from that of styrene-based polymers. The ratio of the total peak area shown in the material is expressed in %.

[equation 1] Homopolymer fraction (area%)=area of homopolystyrene peak∕(area of polystyrene block peak+area of homopolystyrene peak)×100(%)

GPC conditions

- Column: PL Olexis

- Solvent: TCB (trichlorobenzene)

- Flow rate: 1.0 ml/min

- Sample concentration: 1.0 mg/ml

- Injection volume: 200㎕

- Column temperature: 160°C

- Detector: Agilent high temperature RI detector

- Standard: polystyrene

[Table 2]

Experimental example 2

1) Tensile Strength, Elongation, and 300% Modulus

According to the tensile test method of ASTM D412, use the block copolymers that make among the above examples 1 to 8 and comparative examples 1 to 4 to make samples respectively, and measure the tensile strength, elongation, and 300% modulus.

2) Transparency (turbidity)

Using each of the block copolymers prepared in the above Examples 1 to 8 and Comparative Examples 1 to 4, a film (film thickness 140 μm) was produced using an E20T cast film forming machine of Collin Co., Ltd. under the following conditions, The haze of the film was then measured according to the ISO 14782 standard. At this time, each sample was measured 10 times, and the average value was obtained.

[Film forming conditions]

Screw rpm: 70 rpm

Processing temperature: 210 to 230°C

Cooler: 25°C

Mold: 100mm

[table 3]

As shown in Table 3, the block copolymers of the examples have excellent tensile strength and elongation and also exhibit a moderate degree of 300% modulus value, so it can be confirmed that all the tensile properties are excellent higher than some degree.

In comparison, it can be confirmed that the copolymers of the comparative examples that do not meet all the above conditions are inferior in all aspects of tensile strength, tensile property of elongation, and 300% modulus.

From this result, it can be confirmed that the fraction of polystyrene homopolymer to polystyrene block is 4% or less, and the weight average molecular weight (Mw) measured from gel permeation chromatography (GPC) The multi-block copolymer of the present invention having a condition of 100,000 to 300,000 g/mol has excellent tensile strength and elongation and also exhibits a moderate degree of 300% modulus value, so that all tensile properties are excellent.

Claims (14)

A multi-block copolymer comprising a polystyrene-based block comprising a repeating unit derived from an aromatic vinyl-based monomer and one of a repeating unit derived from ethylene and a repeating unit derived from an α-olefin-based monomer polyolefin block, wherein the fraction of the polystyrene homopolymer relative to the polystyrene block as measured by gel permeation chromatography (GPC) represented by the following equation 1 is 4% or less; and The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 100,000 to 300,000 g/mol, [equation 1] Homopolymer fraction (area %)=area of homopolystyrene peak/(area of polystyrene-based block peak+area of homopolystyrene peak)×100(%). Such as the multi-block copolymer of claim 1, wherein the α-olefin monomer system is selected from one or more of the following groups: 1-hexene, 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. The multi-block copolymer of claim 1, wherein the polystyrene homopolymer measured by the gel permeation chromatography (GPC) is 3.80% or less relative to the polystyrene-based block . The multi-block copolymer as claimed in claim 1, wherein the molecular weight distribution measured by the gel permeation chromatography (GPC) is 1.5 to 3.0. Such as the multi-block copolymer of claim 1, wherein the content of repeating units derived from α-olefin monomers is 10mol by ¹ H NMR (500 MHz, tetrachloroethane-d2, standard TMS) spectrum measurement % to 20mol%. Such as the multi-block copolymer of claim 1, wherein the content of repeating units derived from α-olefin monomers is 20 by ¹ H NMR (500 MHz, tetrachloroethane-d2, standard TMS) spectrum measurement % by weight to 40% by weight. A method of manufacturing the multi-block copolymer as claimed in claim 1, the method comprising: (S1) using an organozinc compound as a chain transfer agent, in the presence of a catalyst composition including a transition metal compound, to prepare a polyolefin-based block by reacting ethylene and an α-olefin-based monomer; and (S2) In the presence of an anionic polymerization initiator, a multi-block copolymer is produced by reacting an aromatic vinyl monomer with a polyolefin block. The method as claimed in item 7, wherein the transition metal compound is a compound represented by the following formula 1: [Formula 1] Wherein in the above formula 1, M is Ti, Zr, or Hf, R ₁ to R ₄ 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, wherein two or more adjacent ones can be connected to each other and form a ring, _R5 and _R6 are each independently hydrogen, substituted or unsubstituted Substituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl, wherein the substitution is carried out by C1 to C12 alkyl, R ₇ Each is independently substituted or unsubstituted C4 to C20 alkyl, substituted or unsubstituted C4 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl, n is 1 to 5 , and Y ₁ and Y ₂ are each independently halo, substituted or unsubstituted C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C3 to C20 cycloalkyl, C6 to C20 aromatic C7 to C20 alkaryl, 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. The method as claimed in item 7, wherein the organozinc compound is represented by the following formula 5: [Formula 5] Wherein in the above formula 5, R ₈ and R ₁₀ are each independently a single bond or a C1 to C10 alkylene group, R ₉ is a C1 to C10 alkylene group or -SiR ₁₁ R ₁₂ -, and R ₁₁ and R ₁₂ are each independently C1 to C10 alkyl. The method according to claim 9, wherein the organozinc compound is prepared by reacting a Grignard reagent containing a styrene moiety with an alkyl zinc alkoxide. The method as claimed in item 10, wherein the Grignard reagent containing a styrene moiety is represented by the following formula 7: [Formula 7] Wherein in the above formula 7, R ₈ and R ₁₀ are each independently a single bond or a C1 to C10 alkylene group, R ₉ is a C1 to C10 alkylene group or -SiR ₁₁ R ₁₂ -, R ₁₁ and R ₁₂ are each independently R is C1 to C10 alkyl, and X is halo. The method as claimed in item 7, wherein the catalyst composition further comprises a compound represented by the following formula 9: [formula 9] Wherein in the above formula 9, each R _a is independently a halogen group, a C1 to C20 hydrocarbon group, or a C1 to C20 hydrocarbon group substituted by a halogen, and m is an integer of 2 or more. The method according to claim 7, wherein the anionic polymerization initiator comprises an allyl group-containing alkyllithium compound, wherein the allyl group is combined with lithium. The method as claimed in item 12, wherein the alkyllithium compound is represented by the following formula 11: [Formula 11] wherein in the above formula 11, R ₁₃ is hydrogen or a C1 to C20 hydrocarbon, and Am is an amine compound represented by the following formula 12: [Formula 12] Wherein in the above formula 12, R ₁₄ to R ₁₈ are each independently hydrogen or a C1 to C20 hydrocarbon, and a and b are each independently an integer from 0 to 3, wherein the a and the b are not 0 at the same time.