WO2019190287A1 - Block copolymer composition - Google Patents

Abstract

The present invention relates to a block copolymer composition comprising a diblock copolymer and a triblock copolymer, which comprise a polyolefin-based block and a polystyrene-based block, wherein the amount of the diblock copolymer is 19 wt% or less, the polyolefin-based block comprises a repeating unit of the following chemical formula 1, and the polystyrene-based block comprises one or more selected from the group consisting of the following chemical formulas 2 and 3.

Description

Block copolymer composition

[Cross-cited with Related Applications]

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0037549 dated March 30, 2018 and Korean Patent Application No. 10-2018-0117841 dated October 02, 2018. All content disclosed in the literature is included as part of this specification.

[Technical Field]

The present invention relates to a block copolymer composition, and more particularly, to a block copolymer composition comprising a diblock copolymer and a triblock copolymer comprising an olefinic polymer block and a styrene polymer block.

Polyolefin-polystyrene block copolymers such as styrene-ethylene / butylene-styrene (SEBS) or styrene-ethylene / propylene-styrene (SEPS) currently have a market of several hundred thousand tons worldwide. In addition, they have the advantages of excellent heat resistance and light resistance compared to styrene-butadiene-styrene (SBS) or styrene-isoprene-styrene (SIS), soft and strong touch of grip and handle, elastic material of diaper, medical and Oil-gels used in communication materials, impact modifiers in engineering plastics, flexibilizers or tougheners in transparent polypropylene, and the like. Conventional SEBS is prepared through a two-step reaction of hydrogenating SBS obtained by anionic polymerization of styrene and butadiene. Conventional SEPS is similarly prepared through a two-step reaction of hydrogenating SIS obtained by anionic polymerization of styrene and isoprene. As such, the process of saturating all the double bonds contained in the polymer main chain by saturating the process cost is high, and the cost of SEBS and SEPS is significantly higher than that of SBS and SIS before the hydrogenation reaction. This may limit market expansion. In addition, it is virtually impossible to saturate all of the double bonds in the polymer chain via hydrogenation, so commercialized SEBS and SEPS contain some residual double bonds and their presence is often a problem (Journal of Polymer Science: Part A: Polymer Chemistry, 2002, 40, 1253; Polymer Degradation and Stability 2010, 95, 975). In addition, the conventional block copolymer prepared in two steps as described above is very limited because the polyolefin block is formed through a hydrogenation reaction after the anionic polymerization of butadiene or isoprene.

Under these backgrounds, the production of polyolefin-polystyrene block copolymers in one-pot reactions directly from olefin monomers and styrene monomers is a challenging research topic with very high commercial ramifications. In this regard, conventionally, by using para-methylstyrene as a molecular weight regulator in the process of propylene polymerization of para-methyl styrene, a polypropylene having para-methyl styryl group is synthesized in the terminal, followed by dehydrogenation of the methyl group of the terminal with butyllithium. An example of preparing a polypripropylene-polystyrene block copolymer by inducing styrene anion polymerization after inducing a reaction has been reported (J. Am. Chem. Soc. 2001, 123, 4871; Macromolecules 2002, 35, 1622). As another example, attempts have been made to prepare block copolymers by performing ethylene / propylene copolymerization using phenoxyimine catalysts and subsequently injecting styrene monomer (Marcomole. Rapid. Commun., 2006, 27). , 1009). However, the conventionally reported methods are not applied to commercial processes due to problems such as a multi-step process required.

The problem to be solved of the present invention is to provide a block copolymer composition comprising a diblock copolymer and a triblock copolymer comprising an olefin-based polymer block and a styrene-based polymer block.

In order to solve the above problems, the present invention includes a diblock copolymer and a triblock copolymer including an olefin polymer block and a styrene polymer block, and the content of the diblock copolymer is 19 wt% or less, and the olefin The polymer block includes a repeating unit represented by Chemical Formula 1, and the styrene-based polymer block provides a block copolymer composition including at least one selected from the group consisting of Chemical Formula 2 and Chemical Formula 3 below.

[Formula 1]

[Formula 2]

[Formula 3]

R ₁ is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl,

R ₂ and R ₃ are each independently aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,

n is an integer from 1 to 10,000,

l and m are each independently an integer of 10 to 1,000.

The block copolymer composition according to the present invention includes a diblock copolymer and a triblock copolymer including an olefinic polymer block and a styrene polymer block, and the structure and properties of each block included in these copolymers are controlled and improved. It can exhibit physical properties.

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

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

The term 'composition' as used herein includes a mixture of materials comprising the composition as well as reaction and decomposition products formed from the material of the composition.

As used herein, the term 'residual unsaturated bond' refers to an unsaturated bond, such as a double bond, a triple bond, present in the polymer chain of the block copolymer included in the block copolymer composition, and the polymer chain is a block copolymer. It includes the main chain and branched chain of, and includes unsaturated bonds generated in the polymerization process as well as unsaturated bonds contained in or derived from raw materials such as monomers, multimers, initiators, catalysts and the like used to prepare the block copolymer do.

As used herein, the term "halogen" means fluorine, chlorine, bromine or iodine, unless stated otherwise.

As used herein, the term 'alkyl' means a straight, cyclic or branched hydrocarbon moiety unless stated otherwise.

As used herein, the term 'aryl' refers to aromatic groups including phenyl, naphthyl anthryl, phenanthryl, chrysenyl, pyrenyl, and the like, unless stated otherwise.

In the present specification, silyl may be silyl unsubstituted or substituted with alkyl having 1 to 20 carbon atoms, for example, silyl, trimethylsilyl or triethylsilyl.

The block copolymer composition of the present invention comprises a diblock copolymer and a triblock copolymer comprising an olefin-based polymer block and a styrene-based polymer block, and the content of the diblock copolymer is 19 wt% or less, and the olefin-based The polymer block includes repeating units represented by Formula 1, and the styrene-based polymer block includes at least one selected from the group consisting of Formula 2 and Formula 3 below.

[Formula 1]

[Formula 2]

[Formula 3]

R ₁ is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl,

R ₂ and R ₃ are each independently aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,

n is an integer from 1 to 10,000,

l and m are each independently an integer of 10 to 1,000.

In the formulas shown in the present specification, "*" represents a linking site as a terminal site of a repeating unit.

In one example of the present invention, R ₁ is hydrogen; Or alkyl having 3 to 12 carbon atoms.

In one example of the present invention, R ₂ and R ₃ are each independently phenyl; Or phenyl unsubstituted or substituted with halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, or aryl having 6 to 12 carbon atoms, wherein R ₂ is hydrogen; Alkyl having 3 to 20 carbon atoms; Alkyl having 3 to 20 carbon atoms substituted with silyl; Arylalkyl having 8 to 20 carbon atoms; Or arylalkyl having 8 to 20 carbon atoms substituted with silyl.

In addition, R ₂ may be hydrogen or alkyl having 4 to 12 carbon atoms, and R ₂ and R ₃ may be phenyl.

N is an integer of 10 to 10,000, specifically may be an integer of 500 to 7,000, and m is an integer of 10 to 1,000, specifically may be an integer of 50 to 700. When n and m satisfy the above range simultaneously, the block copolymer may exhibit both high tensile strength and high elastic modulus.

The l may be an integer of 10 to 1,000, specifically, may be an integer of 50 to 700, and when the l is in the above range, the viscosity of the block copolymer may have an appropriate level.

In one example of the present invention, when the olefinic polymer block includes two or more repeating units represented by Formula 1, the olefinic polymer block may include a repeating unit represented by the following Formula 4.

[Formula 4]

In Chemical Formula 4,

R ₁ ′ and R ₁ ″ each independently represent hydrogen, alkyl having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl; R ₁ 'and R ₁ "are different from each other,

0 <P <1,

n 'may be an integer from 10 to 10,000.

In addition, in one example of the present invention, R ₁ ′ and R ₁ ″ may each independently be hydrogen or alkyl having 3 to 20 carbon atoms, specifically, each independently hydrogen or alkyl having 3 to 12 carbon atoms, More specifically, each may independently be hydrogen or alkyl having 4 to 12 carbon atoms.

Also specifically, n ′ may be an integer of 10 to 10,000, and more specifically, an integer of 500 to 7,000.

In an example of the present invention, in Formula 4, any one of R ₁ ′ and R ₁ ″ may be hydrogen, and the other one may be a substituent other than hydrogen.

That is, in the example of the present invention, the olefin polymer block in this case comprise a repeating unit of two or more kinds represented by the above formula 1, R ₁ having 1 to 20 carbon atoms of any other structure and R ₁ is hydrogen hydrogen alkyl ; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or a silyl group of a carbon number of arylalkyl is a structure of 7 to 20 may be connected at random (random), specifically, R ₁ is an alkyl structure of the structure and R ₁ is 3 to 20 carbon atoms other than a hydrogen hydrogen substituted with May be randomly connected.

In more detail, the olefin-based polymer block may be one in which the structure in which R ₁ is hydrogen and the structure in which R ₁ is alkyl having 3 to 12 carbon atoms in Formula 1 is randomly connected, and more specifically, the olefin-based polymer block. The polymer block may be one in which the structure in which R ₁ is hydrogen and the structure in which R ₁ is alkyl having 4 to 12 carbon atoms in Chemical Formula 1 are randomly connected.

When the olefinic polymer block includes two or more repeating units represented by Formula 1, the olefinic polymer block has a structure in which R ₁ is hydrogen in Formula 1 and R ₁ has a substituent other than hydrogen. It may be included in a weight ratio of 30:90 to 70:10, specifically, may be included in a weight ratio of 40:60 to 60:40, and more specifically may be included in a weight ratio of 45:75 to 55:25.

When comprise a structure wherein the olefin-based polymer block is a R ₁ is hydrogen in the structure and R ₁ in formula (I) having a substituent other than hydrogen in the above range, the branch (branch) suitable degree in the block copolymer of the structure to be produced Since it has a high modulus value and elongation at break value of 300%, it can exhibit excellent elastic properties, and also exhibit a wide molecular weight distribution with high molecular weight, thereby having excellent processability.

In one example of the present invention, the diblock copolymer and the triblock copolymer may each include a composite block represented by the following Formula 5 formed by combining the polyolefin block and the polystyrene block.

[Formula 5]

In Chemical Formula 5,

R ₁ is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl,

R ₂ is aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,

l is an integer from 10 to 1,000,

n is an integer from 10 to 10,000.

In addition, in Formula 5, R ₁ , R ₂ , l and n are as defined in Formula 1 or Formula 2, respectively.

In addition, in one example of the present invention, when the olefin-based polymer block includes a repeating unit represented by Formula 4, the composite block formed by combining the polystyrene-based block may be represented by the following formula (6).

[Formula 6]

In Formula 6, R ₁ ', R ₁ ", p, l and n' are as defined in Formula 2 or 4, respectively.

In the present specification, the olefin-based polymer block including the repeating unit represented by Formula 1 is also represented as a first block, and each of the styrene-based polymer blocks including the repeating unit represented by Formulas 2 and 3 is a second block. And third block.

In one example of the present invention, when two or more of the first block and the second block are included, the first block and the second block may be included as a repeating unit of a complex block having a structure represented by Formula 5 or 6 above. For example, when the block copolymer composition according to an example of the present invention includes a block copolymer including two first blocks, two second blocks, and one third block, the block copolymer Means that it contains two composite blocks and one third block.

In addition, in one example of the present invention, when the block copolymer includes two or more complex blocks of Formula 5 or 6, the remaining complex blocks except for one complex block is connected to the other complex block, and May not be connected. For example, when the block copolymer includes two or more of the composite blocks, one composite block is connected to the third block, and the composite block extends through a bond between the composite blocks to form a "third block-composite block-". Composite block-… ".

In addition, when two composite blocks are connected, the first block and the second block included in the composite block may be connected. For example, the block copolymer according to an example of the present invention may include one third block and two composite blocks. If so, the structure may have a structure such as "third block-first block-second block-first block-second block-".

As such, the block copolymer composition according to the exemplary embodiment of the present invention may include a block copolymer including a structure represented by the following Formula 7, specifically, a triblock copolymer.

[Formula 7]

In Chemical Formula 7,

R ₁ is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl,

R ₂ and R ₃ are each independently aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,

l and m are each independently an integer of 10 to 1,000,

n is an integer from 10 to 10,000.

In addition, in Formula 5, a may be an integer of 1 to 50, specifically, an integer of 1 to 20, and more specifically, an integer of 1 to 10.

In addition, R ₁ is hydrogen; Alkyl having 1 to 13 carbon atoms; Alkyl having 1 to 13 carbon atoms substituted with silyl; Arylalkyl having 7 to 13 carbon atoms; Or arylalkyl having 7 to 13 carbon atoms substituted with silyl,

R ₂ may be unsubstituted or substituted with halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, or aryl having 6 to 12 carbon atoms,

R ₃ is hydrogen; Or alkyl having 1 to 12 carbon atoms.

In addition, in Formula 7, R ₁ to R ₃ , l, m, and n are the same as defined in Chemical Formulas 1 to 3, respectively.

In addition, the block copolymer composition according to an embodiment of the present invention may include a block copolymer, specifically a triblock copolymer, having a structure represented by the following formula (8).

[Formula 8]

In Chemical Formula 8,

R ₁ ′ and R ₁ ″ each independently represent hydrogen, alkyl having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl, wherein R ₁ 'and R ₁ "are different from each other,

0 <p <1,

R ₂ and R ₃ are each independently aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,

l and m are each independently an integer of 10 to 1,000,

n is an integer from 10 to 10,000,

a is an integer of 1-50.

In Formula 8, R ₁ ′, R ₁ ″, p, l, n ′, a are the same as defined in Formula 2, 4, or 7, respectively.

The composition of the block copolymer of the present invention may include, for example, (1) reacting an organic zinc compound with at least one olefinic monomer under a transition metal catalyst to form an olefinic polymer block to prepare an intermediate; And (2) reacting the intermediate obtained in step (1) with a styrene monomer in the presence of an alkyllithium compound to form a styrene polymer block.

The compound prepared in step (2) may be an organic zinc compound comprising a block copolymer comprising the repeating unit structure of Chemical Formulas 1 to 3 above, and additionally, the product prepared in step (2) is water (3). It can be converted to the block copolymer by the step of reacting with oxygen, or an organic acid to convert into a block copolymer.

(1) preparing an intermediate by reacting an organozinc compound with at least one olefinic monomer under a transition metal catalyst to form an olefinic polymer block.

In the step (1), the olefinic monomer may be inserted between Zn and A of the organic zinc compound to polymerize and form an olefinic polymer block including a repeating unit represented by Chemical Formula 1.

In one example of the present invention, the olefinic monomer which is inserted between Zn and A of the organic zinc compound to polymerize to form the olefinic polymer block (first block) comprises ethylene and at least one alpha-olefinic monomer. It may be included together, and specifically may include ethylene and one or more alpha-olefin monomers other than ethylene. In one example of the present invention, the olefinic monomer which is inserted between Zn and A of the organic zinc compound to polymerize to form the olefinic polymer block (first block) comprises ethylene and at least one alpha-olefinic monomer. It may be included together, and specifically may include ethylene and one or more alpha-olefin monomers other than ethylene.

In one example of the present invention, the alpha-olefin monomer may be specifically an aliphatic olefin having 3 to 20 carbon atoms, more specifically an aliphatic olefin having 4 to 12 carbon atoms, and more specifically an aliphatic olefin having 5 to 12 carbon atoms. have. Examples of the aliphatic olefins include propylene, 1-butene, 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 or 3,4-dimethyl-1-hexene, and the like, and any one or a mixture of two or more thereof.

In one embodiment of the present invention, the organic zinc compound may be a compound represented by the following formula (9).

[Formula 9]

In Chemical Formula 9,

A is alkylene having 1 to 20 carbon atoms; Arylene having 6 to 20 carbon atoms; Or arylene having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,

B is arylene having 6 to 12 carbon atoms substituted with alkenyl having 2 to 12 carbon atoms.

In addition, A is an alkylene having 1 to 12 carbon atoms; Arylene having 6 to 12 carbon atoms; Or arylene having 6 to 12 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,

B may be arylene having 6 to 12 carbon atoms substituted with alkenyl having 2 to 8 carbon atoms.

Formula 9 may have a structure in which both ends of the formula is a double bond, for example, when B is arylene substituted with alkenyl, the arylene is linked to A, and a double of alkenyl substituted with arylene The bond may be located at the outermost part of the formula (3).

When the organic zinc compound is reacted with at least one olefinic monomer for forming the first block as described above under a transition metal catalyst for olefin polymerization, zinc (Zn) and organic group (A) of the organic zinc compound Polymerization is performed while the olefinic monomer is inserted therebetween, thereby preparing an intermediate in which an olefinic polymer block (first block) is formed. One example of the intermediate formed in this way is shown in the following formula (10).

[Formula 10]

In Chemical Formula 10,

R ₁ is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl,

A is alkylene having 1 to 20 carbon atoms; Arylene having 6 to 20 carbon atoms; Or arylene having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,

B is arylene having 6 to 12 carbon atoms substituted with alkenyl having 2 to 12 carbon atoms,

n is an integer from 10 to 10,000.

In addition, R ₁ and n are as defined in Formula 1, respectively, and A and B are as defined in Formula 9, respectively.

In one example of the present invention, when the organic zinc compound is reacted with two or more kinds of olefinic monomers for forming the first block as described above under a transition metal catalyst for olefin polymerization, an example of the intermediate formed is It can be represented as 11.

[Formula 11]

In Formula 11, R ₁ ′, R ₁ ″, p and n ′ are as defined in Formula 2, respectively, and A and B are as defined in Formula 9, respectively.

(2) reacting the intermediate obtained in step (1) with a styrene monomer in the presence of an alkyllithium compound to form a styrene polymer block

In the step (2), the styrene-based monomer is inserted between the Zn and the olefin-based polymer block of the intermediate may be polymerized to form a styrene-based polymer block.

The alkyllithium may be an alkyllithium compound including a silicon atom, for example Me ₃ SiCH ₂ Li.

In the step (2), the styrene monomer is inserted between Zn of the intermediate and the olefin polymer block to polymerize and form a styrene polymer block (second block), thereby repeating unit represented by the formula (1) A complex block represented by Chemical Formula 5 may be formed by combining a first block including and a second block including a repeating unit represented by Chemical Formula 2.

In one example of the present invention, in the step (2), the styrene-based monomer is inserted between the Zn and the olefin-based polymer block of the intermediate to form a styrene polymer block (second block) while polymerization is carried out In addition, the styrene-based monomer may be bonded to a portion represented by B of the organic zinc compound represented by Formula 9 to polymerize to form a separate styrene-based polymer block. In the present specification, a separate styrene-based polymer block bonded to the portion represented by B is polymerized as a third block, which corresponds to a repeating unit represented by Chemical Formula 3.

In the manufacturing method according to an embodiment of the present invention, since the first block, the second block and the third block are symmetrically formed around the zinc (Zn) of the organic zinc compound represented by Formula 9, the step (2 ), A compound in which a triblock copolymer comprising three blocks around zinc is symmetrically formed can be prepared. An example of such a block copolymer is represented by the following formula (12).

[Formula 12]

In Chemical Formula 12,

R ₁ to R ₃ , l, m and n are each as defined in Chemical Formulas 1 to 3, A is as defined in Chemical Formula 9, and B 'is a repeating unit of Chemical Formula 3, wherein B' is defined in Chemical Formula 9. It is combined with.

In addition, when the first block includes a repeating unit represented by the formula (4), an example of a compound in which a triblock copolymer including three blocks symmetrically formed based on zinc prepared in the step (2) May be represented by the following Chemical Formula 13.

[Formula 13]

In Chemical Formula 13,

R ₁ ′, R ₁ ″, R ₂ and R ₃ , p, l, m and n ′ are as defined in Formulas 2, 3 and 4, respectively, A is as defined in Formula 9, and B ′ is B defined in Chemical Formula 9 represents a form combined with a repeating unit of Chemical Formula 3.

In one example of the present invention, the styrene monomer is, for example, styrene unsubstituted or substituted with halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms. It may be a system monomer.

As described above, the third block is formed at the same time as the second block is formed in the step (2), so that a triblock copolymer can be formed, and the second block or the third block is formed in the step (2). If no formation of any of the blocks is made, a diblock copolymer is formed.

The block copolymer composition of the present invention comprises a polystyrene-polyolefin-polystyrene triblock copolymer and a polyolefin-polystyrene diblock copolymer, wherein the content of the diblock copolymer is 19% by weight or less. The content of the polyolefin-polystyrene diblock copolymer and polystyrene-polyolefin-polystyrene triblock copolymer is determined by the number of moles of the organic zinc compound used in step (1) and the number of moles of alkyllithium compound used in step (2). Affected by rain

When the number of moles of the alkyllithium compound used in the step (2) when preparing the block copolymer composition of the present invention has a larger value than the number of moles of the organic zinc compound used in the step (1), that is, When the amount of lithium (Li) used in the manufacturing process of the block copolymer composition of the present invention is higher than that of zinc (Zn), the polymerization rate is further increased to increase the productivity, and both the zinc (Zn) and the olefin-based polymer terminals are started ( initiation) to effectively synthesize the triblock copolymer to increase the content of the triblock copolymer in the composition.

On the other hand, the number of moles of the alkyllithium compound used in the step (2) is not particularly limited as long as it has a large value compared to the number of moles of the organic zinc compound used in the step (1), the organic used in the step (1) The number of moles of the zinc compound and the number of moles of the alkyllithium compound used in the step (2) may be 1: 1.05 to 1: 4, specifically 1: 1 to 1: 3, more specifically 1.1 to 2.5 days Can be.

The block copolymer composition of the present invention may include the diblock copolymer in the copolymer composition in an amount of 19 wt% or less, specifically 18 wt% or less, and more specifically 17 wt% or less. Since the mechanical properties of the copolymer composition may decrease as the content of the diblock copolymer increases, the smaller the content of the diblock copolymer is, the better, but the lower limit of the content of the diblock copolymer may be 0.1% by weight. In one example of the present invention, the diblock copolymer may include a structure of Formula 5 or 6, and the triblock copolymer may include a structure of Formula 7 or 8. In addition, the diblock copolymer has a structure of a CH ₃ form in which a unit derived from an organic zinc compound of Formula 9, that is, B and A defined in Formula 9, is bonded to one end of Formula 5 or 6, and the other end is terminated. It may have, and the triblock copolymer may have a structure of Formula 7 or 8.

In one example of the present invention, in step (2), an amine compound, specifically a triamine compound, may be used together with the alkyllithium compound, and the triamine compound may be, for example, PMDETA (N, N, N ″, N ″). , N "-pentamethyldiethylenetriamine). The alkyllithium compound and the amine compound may be used, for example, in a molar ratio of 0.5: 1 to 1: 1. The amine compound may act as an initiator in combination with the alkyllithium compound. Can be.

The block copolymer composition of the present invention may include 10% by weight to 99% by weight of the polyolefin-based block, based on the entire composition, and may include 1% by weight to 90% by weight of the polystyrene-based block. In addition, in detail, the polyolefin block may include 40 wt% to 85 wt%, and the polystyrene block may include 15 wt% to 60 wt% in total, and more specifically, the polyolefin block 60 It may include a weight% to 80% by weight, and may comprise 20% to 40% by weight of the total polystyrene-based block.

The block copolymer composition according to the exemplary embodiment of the present invention may include a structure including a compound used in the preparation process between the third block and the first block, specifically, a unit derived from the organic zinc compound represented by Chemical Formula 9 above. It may be. An example of such a block copolymer structure is shown in the following formula (14).

[Formula 14]

In Formula 14, R ₁ to R ₃ , l, m, n, and a are as defined in Formulas 1 to 3 and 7, respectively, A is as defined in Formula 9, and B 'is defined in Formula 9 above. B represents the form combined with the repeating unit of Formula (3).

In addition, another example of a block copolymer structure in which a compound derived from the compound used in the preparation process, specifically, the organic zinc compound of Formula 9, is included between the third block and the first block may be represented as in Formula 15 below. Can be represented.

[Formula 15]

In Chemical Formula 15,

R ₁ ′, R ₁ ″, R ₂ and R ₃ , p, l, m, n ′ and a are as defined in Formulas 2 to 4 and 7, respectively, A is as defined in Formula 9, B 'represents a form in which B defined in Chemical Formula 9 is combined with a repeating unit represented by Chemical Formula 3.

In the block copolymer composition according to the exemplary embodiment of the present invention, a compound including a block copolymer symmetrically formed around zinc is prepared using the organic zinc compound, and then water, oxygen, or an organic acid is added thereto. It is produced by a manufacturing method that includes a process, and does not require a saturation step of hydrogenating the block copolymer separately, and thus by a one-pot production method in which the saturation process of hydrogenating the block copolymer is omitted separately. It has the advantage of being done.

In addition, the block copolymer composition of the present invention does not use a monomer that can leave a residual unsaturated bond, such as a diene compound such as butadiene or isoprene in the manufacturing process of the polyolefin-based block containing, in the saturation process to hydrogenate it There is no problem that an unsaturated bond which is not saturated also remains.

The block copolymer composition of the present invention prepared as described above may have a weight average molecular weight of 58,000 g / mol to 500,000 g / mol, specifically, a weight average molecular weight of 60,000 g / mol to 300,000 g / mol, more specifically 65,000 It may have a weight average molecular weight of g / mol to 200,000 g / mol.

The block copolymer composition may have a polydispersity index (PDI) value of greater than 1.1 but less than or equal to 3, specifically 1.2 to 2.5, and more specifically 1.3 to 1.8.

The block copolymer composition may have a tensile strength of 30 MPa or less, specifically 5 MPa to 28 MPa, and more specifically 10 MPa to 26 MPa.

In addition, the block copolymer composition may have a 300% modulus value of 2 MPa to 15 Mpa, specifically 2.5 MPa to 10 MPa, and more specifically 3 MPa to 8 MPa.

In addition, the block copolymer composition may have an elongation at break of 800% to 2,000%, specifically 850% to 1,500%, and more specifically 870% to 1,300%.

Example

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

Preparation Example: Preparation of Organic Zinc Compound

[Formula 16]

Borane dimethyl sulfide (1.6 mL, 3.2 mmol) was slowly added to triethylborane (0.6 g) under stirring, followed by reaction for 90 minutes. The solution was slowly added to divinylbenzene (3.8 g) dissolved in anhydrous diethyl ether (10 mL) cooled to -20 ° C, and then stirred overnight. The solvent was removed with a vacuum pump and then diethyl zinc (0.8 g) was added. The reaction was carried out while removing triethyl borane produced by distillation under reduced pressure at 0 ° C. for 5 hours. At 40 ° C. excess divinylbenzene and diethylzinc were removed by distillation under reduced pressure. Methylcyclohexane (150 mL) was added to dissolve the product again, and the solid compound produced as a by-product was filtered off using celite to prepare an organic zinc compound represented by Chemical Formula 16.

Example 1

15 mL of 1-hexene and 240 μmol of an organic zinc compound {(CH ₂ = CHC ₆ H ₄ CH ₂ CH ₂ ) ₂ Zn} were dissolved in 100 g of methylcyclohexane, and the temperature was raised to 80 ° C in a high pressure reactor. .

To as a transition metal compound and co-catalyst of the formula _{17 [(C 18 H 37)} N (Me) H + [B (C 6 F 5) 4] - 1: a solution containing a ratio of 1 (5 μmol ) Was injected into the high pressure reactor and ethylene was immediately injected to maintain a pressure of 20 bar.

After the polymerization process was carried out for 45 minutes at a temperature of 95 ℃ to 100 ℃, the remaining gas was discharged. Me ₃ SiCH ₂ Li and PMDETA (N, N, N ", N", N "-pentamethyldiethylenetriamine) were mixed into methylcyclohexane in a ratio of 1: 1 (420 μmol), injected into the reactor and stirred for 30 minutes. Stirring temperature was maintained at 90 ° C. to 100 ° C. 8.5 mL of styrene was injected into a high pressure reactor and maintained at 90 ° C. to 100 ° C. for 5 hours to convert all of the styrene monomers. , Acetic acid and ethanol were injected continuously The resulting polymer composition was dried overnight in a vacuum oven at 80 ° C.

[Formula 17]

Examples 2-9

Example 1, except that the amount of 1-hexene, styrene, organic zinc compound, methylcyclohexane, transition metal compound / cocatalyst solution, and the amount of Me ₃ SiCH ₂ Li and PMDETA were changed as shown in Table 1 below In the same manner as the polymer composition was prepared.

Comparative Examples 1 to 3

As Comparative Examples 1 to 3, Product # 200565, 200557 and Kraton G1657, manufactured by aldrich, were used as commercially available SEBS.

Comparative Example 4

30 mL of 1-propylene and 150 μmol of an organic zinc compound {(CH ₂ = CHC ₆ H ₄ CH ₂ CH ₂ ) ₂ Zn} were dissolved in 100 g of methylcyclohexane in a high pressure reactor, and the temperature was raised to 80 ° C. .

A solution containing [(C ₁₈ H ₃₇ ) N (Me) H ⁺ [B (C ₆ F ₅ ) ₄ ] ⁻ in a ratio of 1: 1 as a transition metal compound and a cocatalyst represented by Chemical Formula 17 (1 μmol). ) Was injected into the high pressure reactor immediately 30 g of propylene, ethylene was injected to a pressure of 20 bar, and maintained at 20 bar.

After the polymerization process was carried out for 45 minutes at a temperature of 95 ℃ to 110 ℃, the remaining gas was discharged. Me ₃ SiCH ₂ Li and PMDETA (N, N, N ", N", N "-pentamethyldiethylenetriamine) were mixed into methylcyclohexane in a ratio of 1: 1 (150 μmol), injected into the reactor and stirred for 30 minutes. The stirring temperature was maintained at 90 ° C. to 110 ° C. 7.8 g of styrene was injected into a high pressure reactor and then maintained at 90 ° C. to 110 ° C. for 5 hours to convert all of the styrene monomers. , Acetic acid and ethanol were injected continuously The resulting polymer composition was dried overnight in a vacuum oven at 80 ° C.

Comparative Example 5

A polymer composition was prepared in the same manner as in Comparative Example 4, except that 35 mL of propylene was injected, ethylene was injected to have a pressure of 20 bar, and 20 bar was maintained.

Comparative Example 6

10 mL of 1-hexene and 150 μmol of an organic zinc compound {(CH ₂ = CHC ₆ H ₄ CH ₂ CH ₂ ) ₂ Zn} were dissolved in 100 g of methylcyclohexane, and the temperature was raised to 80 ° C. .

A solution containing [(C ₁₈ H ₃₇ ) N (Me) H ⁺ [B (C ₆ F ₅ ) ₄ ] ⁻ in a ratio of 1: 1 as a transition metal compound and a cocatalyst represented by Chemical Formula 17 (1 μmol). ) Was injected into the high pressure reactor immediately 30 g of propylene, ethylene was injected to a pressure of 20 bar, and maintained at 20 bar.

After the polymerization process was carried out for 45 minutes at a temperature of 95 ℃ to 110 ℃, the remaining gas was discharged. Me ₃ SiCH ₂ Li and PMDETA (N, N, N ", N", N "-pentamethyldiethylenetriamine) were mixed into methylcyclohexane in a ratio of 1: 1 (150 μmol), injected into the reactor and stirred for 30 minutes. The stirring temperature was maintained at 90 ° C. to 110 ° C. 7.8 g of styrene was injected into a high pressure reactor and then maintained at 90 ° C. to 110 ° C. for 5 hours to convert all of the styrene monomers. , Acetic acid and ethanol were injected continuously The resulting polymer composition was dried overnight in a vacuum oven at 80 ° C.

Comparative Example 7

15 mL of 1-hexene was injected, ethylene was injected to a pressure of 20 bar, and a polymer composition was prepared in the same manner as in Comparative Example 6, except that 20 bar was maintained.

usage Alphaolefin (mL) Styrene (mL) Organic zinc compound (μmol) Methylcyclohexane (g) Transition Metal Compound / Promoter Solution (μmol) Me ₃ SiCH ₂ Li / PMDETA Example 1 1-hexene15 8.5 240 100 5 420 Example 2 1-hexene15 8.5 300 100 5 420 Example 3 1-hexene15 8.5 179 100 5 420 Example 4 1-hexene30 6.5 357 100 5 420 Example 5 1-hexene25 6.5 357 100 5 420 Example 6 1-hexene30 8.5 357 100 5 420 Example 7 1-hexene30 10 357 100 5 420 Example 8 1-hexene50 13 714 200 5 815 Example 9 1-hexene60 13 714 200 5 815 Comparative Example 4 Propylene 30 7.8 150 100 4 150 Comparative Example 5 Propylene 35 7.8 150 100 4 150 Comparative Example 6 1-hexene 10 7.8 150 100 4 150 Comparative Example 7 1-hexene15 7.8 150 100 4 150

Experimental Example

Physical properties of the block copolymers of Examples 1 to 9 and Comparative Examples 1 to 7 were measured according to the following methods, and are shown in Table 2 below.

1) Weight average molecular weight (Mw, g / mol ), Number average molecular weight (Mn, g / mol ) And Polydispersity index (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. The polydispersity index (PDI) was calculated.

Column: PL Olexis

Solvent: Trichlorobenzene (TCB)

Flow rate: 1.0 ml / min

Sample concentration: 1.0 mg / ml

Injection volume: 200 μl

Column temperature: 160 ° C

-Detector: Agilent High Temperature RI detector

-Polystyrene Standard

-Molecular weight calculation by Mark-Houwink equation (K = 40.8 × 10 ^-5 , α = 0.7057), Universal Calibration

2) the content of 1-hexene and branches

Measured by NMR. The 1H NMR was measured using a Bruker 600MHz AVANCE III HD NMR instrument at ns = 16, d1 = 3s, solvent = TCE-d2, 373K, and the TCE-d2 solvent peak was calibrated to 6.0 ppm and 1-butene at 0.92 ppm. CH ₃ of the content was calculated after identifying the CH ₃ related triplet of the butyl branch with 1-hexene at around 0.96 ppm.

3) Measurement of tensile strength, 300% modulus and elongation

Using the polymer composition of Examples 1 to 5, and Comparative Examples 1 to 3 to form a molded article in a dumbbell-shaped specimens in accordance with ASTM D-412, UTM (Universal Testing Machine) apparatus in accordance with ASTM D638 (Model name: 4466 After pulling the cross head speed (500 mm / min) by using an Instron (R) rule, the point at which each specimen is cut was measured. Tensile strength was calculated by the following equation (1). In addition, the elongation (%) was calculated by the following Equation 2, the 300% modulus (stress at 300%) (MPa) measured the tensile strength when the specimen is stretched three times the initial length.

[Equation 1]

[Equation 2]

4) content of diblock copolymer

GPC curves obtained by gel permeation chromatography (GPC) were obtained by deconvolution assuming peaks with two Gaussian curves.

Origin was used as a program for peak deconvolution, Multiple Peak Fit was used for analysis, and specifically, the molecular weight of the Gaussian curve peak was measured as a triblock. As the molecular weight of the copolymer, 75% of the measured molecular weight was assumed to be the molecular weight of the diblock copolymer and allowed to fit into two peaks. The derived area percentage was calculated as weight percentage based on the measured molecular weight.

Furtherance Molecular Weight Properties Diblock Copolymer Content (% by weight) Ethylene (wt%) Branch (wt%) Styrene (wt%) Mw (g / mol) PDI % Elongation Tensile Strength (MPa) 300% modulus (MPa) Example 1 51.5 20.1 28.4 102,700 1.7 1,201 26.4 6.7 14.8 Example 2 55.1 22.0 22.9 82,000 1.6 1,301 22.4 5.5 13.2 Example 3 49.0 21.3 29.7 98,500 1.5 1,253 25.4 5.9 11.8 Example 4 47.7 25.8 26.5 76,700 1.6 1,603 23.4 3.3 13.8 Example 5 50.8 20.7 28.5 77,900 1.6 1,356 30.6 6.2 11.5 Example 6 48.3 27.7 24 78,400 1.7 1,845 24.1 3.5 9.6 Example 7 49.1 20.9 30.1 101,200 1.7 1,139 29.3 6.1 11.8 Example 8 46.9 28.7 24.4 79,700 1.7 1,779 23.0 3.3 13.8 Example 9 48.4 31.6 22.0 76,100 1.9 2,208 21.2 2.4 10.2 Comparative Example 1 40.7 31.9 27.4 45,000 1.1 960 34 1.0 0 Comparative Example 2 41.3 30.8 27.8 57,000 1.1 1,030 33 1.8 0 Comparative Example 3 48.2 39.1 12.7 65,000 1.2 1,710 18 1.5 30 Comparative Example 4 39.3 18.6 42.1 111,000 1.7 850 9.5 4.5 21.7 Comparative Example 5 45.5 22.5 32.0 109,000 1.7 1390 8.2 2.5 20.2 Comparative Example 6 45.2 21.3 33.5 69,000 1.6 802 16.5 7.7 19.8 Comparative Example 7 47.7 16.4 35.9 68,000 1.5 1,294 21.4 5.9 20.9

Referring to Table 1, compared with the SEBS of the polymer compositions of Examples 1 to 9, 300% modulus of elasticity and elongation at break simultaneously exhibit excellent values and polydispersity. It can be seen that the index (PDI) value is relatively high, indicating excellent processability. In addition, the polymer compositions of Examples 1 to 9 exhibited high polydispersity index (PDI) values, 300% modulus of elongation and elasticity, and excellent tensile strength at the same time. It was confirmed that the excellent physical properties that are distinguished from the poor Comparative Examples 4 to 7.

Claims (16)

It comprises a diblock copolymer and a triblock copolymer comprising a polyolefin block and a polystyrene block, the content of the diblock copolymer is 19% by weight or less, The polyolefin block includes a repeating unit of Formula 1, and the polystyrene block is a block copolymer composition comprising at least one selected from the group consisting of Formula 2 and Formula 3: [Formula 1]

[Formula 2]

[Formula 3]

R ₁ is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl, R ₂ and R ₃ are each independently aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, n is an integer from 1 to 10,000, l and m are each independently an integer of 10 to 1,000. The method of claim 1, R ₁ is hydrogen; Alkyl having 3 to 20 carbon atoms; Alkyl having 3 to 20 carbon atoms substituted with silyl; Arylalkyl having 8 to 20 carbon atoms; Or arylalkyl having 8 to 20 carbon atoms substituted with silyl. The method of claim 1, R ₂ and R ₃ are each independently phenyl; Or phenyl unsubstituted or substituted with halogen, alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 12 carbon atoms, alkoxy of 1 to 8 carbon atoms, or aryl of 6 to 12 carbon atoms. The method of claim 1, R ₁ is hydrogen; Or alkyl having 3 to 12 carbon atoms. The method of claim 1, R ₁ is hydrogen or alkyl having 4 to 12 carbon atoms, and R ₂ and R ₃ are phenyl. The method of claim 1, The polyolefin block comprises a block copolymer composition comprising a repeating unit represented by the following formula (4): [Formula 4]

In Chemical Formula 4, R ₁ ′ and R ₁ ″ each independently represent hydrogen, alkyl having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl; R ₁ 'and R ₁ "are different from each other, 0 <P <1, n 'is an integer from 10 to 10,000. The method of claim 1, The diblock copolymer and the triblock copolymer each independently comprise a composite block represented by the following formula (5) formed by combining the polyolefin-based block and the polystyrene-based block, a block copolymer composition: [Formula 5]

In Chemical Formula 5, R ₁ is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl, R ₂ is aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, l is an integer from 10 to 1,000, n is an integer from 10 to 10,000. The method of claim 1, The diblock copolymer and the triblock copolymer each independently comprise a composite block represented by the following formula (6) formed by combining the polyolefin-based block and the polystyrene-based block, a block copolymer composition: [Formula 6]

In Chemical Formula 6, R ₁ ′ and R ₁ ″ each independently represent hydrogen, alkyl having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl; R ₁ 'and R ₁ "are different from each other, R ₂ is aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, 0 <P <1, n 'is an integer from 10 to 10,000, l is an integer from 10 to 1,000. The method of claim 1, The triblock copolymer comprises a block copolymer composition comprising a structure represented by the following formula (7): [Formula 7]

In Chemical Formula 7, R ₁ is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl, R ₂ and R ₃ are each independently aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, l and m are each independently an integer of 10 to 1,000, n is an integer from 10 to 10,000, a is an integer of 1-50. The method of claim 1, The triblock copolymer comprises a block copolymer composition comprising a structure represented by the following formula (8): [Formula 8]

In Chemical Formula 8, R ₁ ′ and R ₁ ″ each independently represent hydrogen, alkyl having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl, wherein R ₁ 'and R ₁ "are different from each other, 0 <p <1, R ₂ and R ₃ are each independently aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, l and m are each independently an integer of 10 to 1,000, n is an integer from 10 to 10,000, a is an integer of 1-50. The method of claim 1, The block copolymer composition includes 10 wt% to 99 wt% of the polyolefin block, and 1 wt% to 90 wt% of the polystyrene block. The method of claim 1, The block copolymer composition has a weight average molecular weight of 58,000 g / mol to 500,000 g / mol, block copolymer composition. The method of claim 1, The block copolymer composition has a molecular weight distribution (MWD, molecular weight density) value of more than 1.1 3 or less. The method of claim 1, The block copolymer composition has a tensile strength of 30 MPa or less, measured based on ISO37 standards. The method of claim 1, The block copolymer composition has a 300% modulus value of 2 MPa to 15 MPa. The method of claim 1, The block copolymer composition has an elongation at break of 800% to 2,000%, block copolymer composition.