Block copolymer, method for producing block copolymer, and resin composition

Abstract

The present invention relates to a block copolymer, and more particularly to a block copolymer capable of improving the low-temperature seal strength, seal initiation temperature, and low-temperature impact strength of a polyolefin resin composition, a method for producing the block copolymer, and a polyolefin resin composition containing the block copolymer.

Description

[Technical Field]

[0001] The present invention claims the benefit of priority based on Korean Patent Application No. 10-2023-0004093, filed on January 11, 2023, and all contents disclosed in the documents of this Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a block copolymer, a method for producing the same, and a resin composition containing the same. [Background technology]

[0003] Polypropylene is widely used as a medical material due to its excellent rigidity and moldability. However, it has the problem of low impact strength. To overcome this problem, a method has been proposed in which a styrene-based thermoplastic elastomer, i.e., styrene-ethylene-butylene-styrene block copolymer (Styrene-Ethylene-Butylene-Styrene; SEBS), which is an elastomer, is used in a polypropylene-based resin composition.

[0004] The wettability of polypropylene-based resin compositions containing such styrene-based thermoplastic elastomers improves as the molecular weight distribution of the styrene-based thermoplastic elastomer broadens. The increased wettability leads to better low-temperature heat seal strength and seal initiation temperature (SIT). Excellent low-temperature seal strength and seal initiation temperature can improve product productivity. However, the broader the molecular weight distribution of the styrene-based thermoplastic elastomer, the lower the low-temperature impact strength of polypropylene-based resin compositions containing it.

[0005] Therefore, in order to apply a polypropylene resin composition to a medical material, it is necessary to improve not only the low-temperature seal strength and the seal initiation temperature but also the low-temperature impact strength. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] KR10-1657925B1 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a block copolymer that can improve all of the low-temperature seal strength, seal initiation temperature, and low-temperature impact strength of a polyolefin resin composition.

[0008] Another object of the present invention is to provide a method for producing the block copolymer.

[0009] Another object of the present invention is to provide a polyolefin resin composition containing the block copolymer. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention provides a block copolymer and a resin composition.

[0011] (1) The present invention provides a block copolymer comprising an aromatic vinyl polymer block and an olefin polymer block, having a weight-average molecular weight (Mw) of 110,000 g / mol or more and 200,000 g / mol or less, and a molecular weight distribution (Mw / Mn) of 2.4 or more and 2.9 or less.

[0012] (2) The present invention provides the block copolymer according to (1) above, wherein the olefin polymer block contains ethylene monomer units and α-olefin monomer units.

[0013] (3) The present invention provides the block copolymer according to (1) or (2) above, wherein the olefin polymer block contains an ethylene monomer unit and an α-olefin monomer unit having 3 to 20 carbon atoms.

[0014] (4) The present invention provides the block copolymer according to (2) or (3) above, wherein the α-olefin monomer is at least one selected from the group consisting of 1-propene, 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, and 3,4-dimethyl-1-hexene.

[0015] (5) The present invention provides the block copolymer according to any one of (1) to (4) above, wherein the block copolymer comprises 10% by weight or more and 20% by weight or less of an aromatic vinyl polymer block and 80% by weight or more and 90% by weight or less of an olefin polymer block.

[0016] (6) The present invention provides the block copolymer according to any one of (1) to (5) above, wherein the block copolymer contains 45% by weight or more and 55% by weight or less of α-olefin monomer units having 3 to 20 carbon atoms.

[0017] (7) The present invention provides the block copolymer according to any one of (1) to (6) above, wherein the block copolymer contains 25% by weight or more and 45% by weight or less of ethylene monomer units.

[0018] (8) The present invention provides the block copolymer according to any one of (1) to (7) above, wherein the block copolymer does not contain an unsaturated double bond.

[0019] (9) The present invention provides a method for producing a block copolymer, comprising: a step (S10) of polymerizing one or more olefin monomers using a catalyst composition containing a transition metal catalyst, an aluminoxane compound, and a trialkylaluminum in the presence of a chain transfer agent to produce an olefin polymer block intermediate; and a step (S20) of adding a polymerization initiator and an aromatic vinyl monomer in the presence of the olefin polymer block intermediate produced in the step (S10) and polymerizing the resulting mixture to produce a block copolymer.

[0020] (10) The present invention provides the method for producing a block copolymer according to (9) above, wherein the trialkylaluminum is trioctylaluminum.

[0021] (11) The present invention provides the method for producing a block copolymer according to (9) or (10) above, wherein the catalyst composition contains an aluminoxane compound and a trialkylaluminum in a molar ratio of 1:0.01 or more and 10.0 or less.

[0022] (12) The present invention provides a resin composition comprising a polyolefin resin and the block copolymer according to any one of (1) to (8) above.

[0023] (13) The present invention provides the resin composition according to (12) above, which contains 40% by weight or more and 80% by weight or less of a polyolefin resin and 20% by weight or more and 60% by weight or less of a block copolymer.

[0024] (14) The present invention provides the resin composition according to (12) or (13) above, wherein the resin composition has an impact strength of 5.0 kgf·m / m or more at −50° C. as measured by ADTM D256.

[0025] (15) The present invention provides the resin composition according to any one of (12) to (14), wherein the resin composition has a seal strength of 0.80 N or more at 90°C measured using a film having a thickness of 80 μm and a width of 25.4 mm using a J&B Universal Sealing Machine Type 5000MB under the following conditions: -Sealing pressure: 0.1N / mm 2 -Sealing time: 0.1 seconds -Cooling time: 99 seconds - Peeling speed: 10mm / sec -Starting temperature: 80℃ -End temperature: 150℃ -Temperature increase: 10℃

[0026] (16) The present invention provides the resin composition according to any one of (12) to (15), wherein the resin composition has a seal strength of 4.50 N or more at 100°C measured using a film having a thickness of 80 μm and a width of 25.4 mm using a J&B Universal Sealing Machine Type 5000MB under the following conditions: -Sealing pressure: 0.1N / mm 2 -Sealing time: 0.1 seconds -Cooling time: 99 seconds - Peeling speed: 10mm / sec -Starting temperature: 80℃ -End temperature: 150℃ -Temperature increase: 10℃

[0027] (17) The present invention provides the resin composition according to any one of (12) to (16) above, wherein the resin composition has a sealing initiation temperature of 96.0°C or less at which the seal strength reaches 3N, as calculated by linear interpolation from the seal strengths at 90°C and 100°C measured under the following conditions using a film having a thickness of 80 μm and a width of 25.4 mm using a J&B Universal Sealing Machine Type 5000MB: -Sealing pressure: 0.1N / mm 2 -Sealing time: 0.1 seconds -Cooling time: 99 seconds - Peeling speed: 10mm / sec -Starting temperature: 80℃ -End temperature: 150℃ -Temperature increase: 10℃ [Effects of the Invention]

[0028] The polyolefin resin composition containing the block copolymer of the present invention is excellent in all of low-temperature seal strength, seal initiation temperature, and low-temperature impact strength, and is therefore particularly suitable as a medical material.

[0029] Furthermore, according to the method for producing a block copolymer of the present invention, a block copolymer having a wide molecular weight distribution can be produced in accordance with the object of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0030] The present invention will now be described in more detail so that the present invention may be more easily understood.

[0031] The terms and words used in the description of the present invention and the claims should not be interpreted in a limited way to their ordinary or dictionary meanings, but should be interpreted in a way that is consistent with the technical idea of ​​the present invention, based on the principle that the inventors can appropriately define the concepts of terms in order to best describe their invention.

[0032] In the present invention, the term "monomer unit" refers to a component, structure, or substance itself resulting from a monomer, and as a specific example, it may refer to a repeating unit formed in a polymer when an input monomer participates in a polymerization reaction during polymerization of the polymer.

[0033] As used herein, the term "composition" includes mixtures of materials comprising the composition as well as reaction products and decomposition products formed from the materials of the composition.

[0034] The present invention provides a block copolymer.

[0035] According to one embodiment of the present invention, the block copolymer may include an aromatic vinyl polymer block and an olefin polymer block, and may have a weight average molecular weight (Mw) of 110,000 g / mol to 200,000 g / mol, and a molecular weight distribution (Mw / Mn) of 2.4 to 2.9.

[0036] According to one embodiment of the present invention, the block copolymer containing an aromatic vinyl polymer block and an olefin polymer block is a multiblock copolymer, and is produced in the presence of a novel additive as described in the method for producing a block copolymer described below.

[0037] According to one embodiment of the present invention, the weight-average molecular weight of the block copolymer may be 110,000 g / mol or more and 200,000 g / mol or less, specifically 110,000 g / mol or more, 115,000 g / mol or more, 120,000 g / mol or more, or 125,000 g / mol or more, and 200,000 g / mol or less, 199,000 g / mol or less, 198,000 g / mol or less, 197,000 g / mol or less, 196,000 g / mol or less, 195,000 g / mol or less, 194,000 g / mol or less, 193,000 g / mol or less, 192,000 g / mol or less, or 191,000 g / mol or less.

[0038] According to one embodiment of the present invention, the molecular weight distribution (Mw / Mn, PDI) of the block copolymer may be 2.4 to 2.9. Specific examples include 2.40 or more, 2.41 or more, 2.42 or more, 2.43 or more, or 2.44 or more, and 2.90 or less, 2.89 or less, 2.88 or less, or 2.87 or less. Here, 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-equivalent molecular weights analyzed by gel permeation chromatography (GPC).

[0039] According to one embodiment of the present invention, the weight-average molecular weight and molecular weight distribution of the block copolymer are intended to improve both the low-temperature seal strength, seal initiation temperature, and low-temperature impact strength of a resin composition containing the block copolymer. By adjusting the weight-average molecular weight within the above range and ensuring a very broad molecular weight distribution, the low-temperature seal strength and seal initiation temperature of the resin composition can be improved, as well as the low-temperature impact strength. If the molecular weight distribution of the block copolymer exceeds the upper limit of the above range, this means that the polymerization reaction mediated by the chain transfer agent during the production of the block copolymer did not proceed sufficiently. In other words, this means that the structure of the block copolymer to be produced was not fully formed in the desired form, resulting in a problem of reduced impact strength of the resin composition containing the block copolymer.

[0040] According to an embodiment of the present invention, the block copolymer may be one in which the olefin polymer block includes a branch chain derived from the main chain.

[0041] According to one embodiment of the present invention, the aromatic vinyl polymer block may be a block formed by polymerization of an aromatic vinyl monomer. The aromatic vinyl monomer for forming the aromatic vinyl polymer block may be at least one selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and a specific example thereof may be styrene.

[0042] According to one embodiment of the present invention, the content of the aromatic vinyl polymer block may be 10% by weight or more and 20% by weight or less, based on the total content of the block copolymer. Specific examples include 10.0% by weight or more, 10.5% by weight or more, 11.0% by weight or more, 11.5% by weight or more, 12.0% by weight or more, 12.5% ​​by weight or more, or 12.7% by weight or more, and 20.0% by weight or less, 19.5% by weight or less, 19.0% by weight or less, or 18.8% by weight or less. Within these ranges, the block copolymer exhibits excellent mechanical properties and processability.

[0043] According to one embodiment of the present invention, the olefin polymer block may contain ethylene monomer units and α-olefin monomer units. Specifically, the olefin polymer block (i.e., poly(ethylene-co-olefin)) may contain ethylene monomer units and C3-20 α-olefin monomer units, and more specifically, ethylene monomer units and C6-8 α-olefin monomer units. When the olefin polymer block contains ethylene monomer units and C3-20 or C6-8 α-olefin monomer units, the olefin polymer block exhibits excellent weather resistance, heat resistance, abrasion resistance, impact resistance, adhesion, transparency, and recyclability, and also has the effect of improving the mechanical properties of a resin composition containing the block copolymer. Meanwhile, the ethylene monomer units and α-olefin monomer units of the olefin polymer block may exist in the form of a random copolymer in the olefin polymer block.

[0044] According to one embodiment of the present invention, the α-olefin monomer forming the α-olefin monomer unit may be at least one selected from the group consisting of 1-propene, 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, and 3,4-dimethyl-1-hexene.

[0045] According to one embodiment of the present invention, the content of the olefin polymer block may be 80% by weight or more and 90% by weight or less, based on the total content of the block copolymer. Specific examples include 80.0% by weight or more, 80.5% by weight or more, 81.0% by weight or more, or 81.2% by weight or more, and 90.0% by weight or less, 89.5% by weight or less, 88.0% by weight or less, 87.5% by weight or less, or 87.3% by weight or less. Within these ranges, the block copolymer exhibits excellent mechanical properties and processability.

[0046] According to one embodiment of the present invention, the content of the α-olefin monomer units having 3 to 20 carbon atoms may be 45% by weight or more and 55% by weight or less, based on the total content of the block copolymer. Specifically, the content of the α-olefin monomer units having 3 to 20 carbon atoms may be 45.0% by weight or more, 45.5% by weight or more, 46.0% by weight or more, 46.5% by weight or more, 47.0% by weight or more, 47.5% by weight or more, 48.0% by weight or more, 48.5% by weight or more, 49.0% by weight or more, or 49.2% by weight or more, based on the total content of the block copolymer. Furthermore, the content within this range may be 55.0% by weight or less, 54.5% by weight or less, 54.0% by weight or less, or 53.5% by weight or less. When the content is within this range, the block copolymer exhibits excellent mechanical properties and processability.

[0047] According to one embodiment of the present invention, when the olefin polymer block contains ethylene monomer units, the content of the ethylene monomer units may be the remainder of the total content of the block copolymer, excluding the content of the aromatic vinyl polymer block and the content of the α-olefin monomer units having 3 to 20 carbon atoms. As a specific example, when the olefin polymer block contains ethylene monomer units, the block copolymer may contain 25% by weight to 45% by weight of ethylene monomer units. More specifically, the content may be 25.0 wt% or more, 26.0 wt% or more, 27.0 wt% or more, 28.0 wt% or more, 29.0 wt% or more, or 29.5 wt% or more, or 45.0 wt% or less, 44.0 wt% or more, 43.0 wt% or less, 42.0 wt% or less, 41.0 wt% or less, 40.0 wt% or less, 39.0 wt% or less, 38.5 wt% or less, or 38.1 wt% or less. When the content is within this range, the block copolymer has excellent mechanical properties and processability.

[0048] According to one embodiment of the present invention, the block copolymer is prepared by the block copolymer preparation method described below. Unlike styrene-ethylene-butylene-styrene (SEBS) block copolymers prepared by hydrogenating styrene-butadiene-styrene block copolymers, the SEBS block copolymers do not require hydrogenation and therefore are clearly distinguishable from styrene-ethylene-butylene-styrene (SEBS) block copolymers prepared by hydrogenating styrene-butadiene-styrene block copolymers in that they do not contain unsaturated double bonds, resulting in excellent polymer stability.

[0049] The present invention provides a method for producing a block copolymer, which is a method for producing the above-mentioned block copolymer.

[0050] According to one embodiment of the present invention, the method for preparing a block copolymer may include the steps of: (S10) polymerizing one or more olefin-based monomers using a catalyst composition including a transition metal catalyst, an aluminoxane-based compound, and a trialkylaluminum in the presence of a chain transfer agent to prepare an olefin-based polymer block intermediate; and (S20) adding and polymerizing a polymerization initiator and an aromatic vinyl-based monomer in the presence of the olefin-based polymer block intermediate prepared in the step (S10) to prepare a block copolymer.

[0051] According to one embodiment of the present invention, the step (S10) is a step of polymerizing one or more olefin-based monomers using a transition metal catalyst in the presence of a chain transfer agent to prepare an olefin-based polymer block intermediate.

[0052] According to one embodiment of the present invention, the transition metal catalyst is a catalyst for growing an olefin polymer by coordination chain transfer polymerization, and may be a catalyst composition including a transition metal catalyst as a main catalyst, a co-catalyst, and a trialkylaluminum.

[0053] According to one embodiment of the present invention, the transition metal catalyst may be a transition metal compound represented by the following Chemical Formula 1:

[0054] [ka]

[0055] In the above Chemical Formula 1, M is Ti, Zr, or Hf; R1 to R4 are each independently hydrogen; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein two or more adjacent groups may be linked to each other to form a ring; R5 and R6 are each independently hydrogen; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein the substitution is with an alkyl group having 1 to 12 carbon atoms; and R7 are each independently a substituted or unsubstituted alkyl group having 4 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 4 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. an aryl group having a prime number of 6 to 20, n being 1 to 5; and Y1 and Y2 each independently represent a halogen group; a substituted or substituted alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 3 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; an alkylaryl group having 7 to 20 carbon atoms; an arylalkyl group having 7 to 20 carbon atoms; a heteroaryl group having 5 to 20 carbon atoms; an alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted aryloxy group having 5 to 20 carbon atoms; an alkylamino group having 1 to 20 carbon atoms; an arylamino group having 5 to 20 carbon atoms; an alkylthio group having 1 to 20 carbon atoms; an arylthio group having 5 to 20 carbon atoms; an alkylsilyl group having 1 to 20 carbon atoms; an arylsilyl group having 5 to 20 carbon atoms; a hydroxy group; an amino group; a thio group; a silyl group; a cyano group; or a nitro group.

[0056] According to one embodiment of the present invention, in Formula 1, M may be Hf, and R1 to R4 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, where two or more adjacent groups may be linked together to form a ring. Alternatively, R1 and R2 are each independently alkyl groups having 1 to 20 carbon atoms, where they are linked together to form an aromatic ring having 5 to 20 carbon atoms, and R3 and R4 are hydrogen.

[0057] According to one embodiment of the present invention, in Chemical Formula 1, R5 and R6 are each independently hydrogen; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and the substitution may be with an alkyl group having 1 to 6 carbon atoms.

[0058] According to one embodiment of the present invention, in Chemical Formula 1, each R7 may independently be a substituted or unsubstituted alkyl group having 4 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 4 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

[0059] According to one embodiment of the present invention, in the above Chemical Formula 1, n may be 1 to 3, preferably 2, and X1 and X2 may each independently be an alkyl group having 1 to 20 carbon atoms.

[0060] According to one embodiment of the present invention, the transition metal compound represented by Chemical Formula 1 may be a compound represented by the following Chemical Formula 1a:

[0061] [ka]

[0062] In the chemical formula 1a, M, R5 to R7, Y1 and Y2 are as defined above.

[0063] According to one embodiment of the present invention, the transition metal compound represented by Chemical Formula 1 may be selected from the following compounds, but is not limited thereto, and all transition metal compounds corresponding to Chemical Formula 1 are included in the present invention.

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] According to one embodiment of the present invention, the transition metal compound represented by Formula 1 may be prepared using a ligand compound represented by Formula 2 below.

[0073] [ka]

[0074] In Chemical Formula 2, R1 to R4 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein two or more adjacent groups may be linked to each other to form a ring; R5 and R6 are each independently a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein the substitution is with an alkyl group having 1 to 12 carbon atoms; R7 are each independently a substituted or unsubstituted alkyl group having 4 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 4 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; and n is 1 to 5.

[0075] According to one embodiment of the present invention, the transition metal compound represented by Chemical Formula 1 may be prepared by reacting a ligand compound represented by Chemical Formula 2 with a compound represented by Chemical Formula 3:

[0076] [ka]

[0077] [Chemical formula 3] M(Y1Y2)2

[0078] In the above formula, R1 to R7, M, Y1, and Y2 are as defined above.

[0079] According to one embodiment of the present invention, the transition metal compound represented by Formula 1 may be prepared through the following reaction process.

[0080] [ka]

[0081] [ka]

[0082] According to one embodiment of the present invention, the organozinc compound is used as a chain transfer agent, which induces chain transfer during polymerization to produce a copolymer, and the chain transfer agent may be a chain transfer agent for producing a block copolymer by coordination chain transfer polymerization.

[0083] According to one embodiment of the present invention, the chain transfer agent may include an organozinc compound represented by the following Chemical Formula 5. Specifically, the chain transfer agent may include 96 mol % or more of the organozinc compound represented by the following Chemical Formula 5, and preferably, may not include any by-products other than the organozinc compound represented by the following Chemical Formula 5.

[0084] [ka]

[0085] In the above Chemical Formula 5, R and R 10 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and R9 is an alkylene group having 1 to 10 carbon atoms or -SiR 11 R 12 - and R 11 and R 12 may each independently be an alkyl group having 1 to 10 carbon atoms.

[0086] According to one embodiment of the present invention, in Formula 5, R and R 10 are each independently a single bond or an alkylene group having one carbon atom, and R9 is an alkylene group having one carbon atom or -SiR 11 R 12 - and R 11 and R 12 may each independently be an alkyl group having one carbon atom.

[0087] According to one embodiment of the present invention, the organozinc compound represented by the formula 5 may be one selected from the group consisting of organozinc compounds represented by the following formulas 5-1 to 5-4, and preferably any one of formulas 5-3 and 5-4.

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] According to one embodiment of the present invention, the chain transfer agent may preferably contain 97 mol% or more, more preferably 98 mol% or more, or 99 mol% or more of the organozinc compound of Chemical Formula 5, and most preferably contain no by-products other than the organozinc compound. This means that it does not contain impurities containing chlorine or magnesium, as well as by-products such as dimers other than the organozinc compound of Chemical Formula 5. In other words, the chain transfer agent may contain only the organozinc compound of Chemical Formula 5.

[0093] According to one embodiment of the present invention, when one or more olefin-based monomers, specifically, ethylene and α-olefin-based monomers, are reacted with the organozinc compound of Formula 5 as a chain transfer agent in the presence of a catalyst composition containing a transition metal compound, zinc (Zn) of the organozinc compound and R 10 The ethylene and α-olefin monomers can be inserted between the two to carry out polymerization.

[0094] According to one embodiment of the present invention, when an olefin polymer block is produced by reacting ethylene and an α-olefin monomer using the compound of Formula 5 as the organozinc compound, an olefin polymer block intermediate is produced, and the olefin polymer block intermediate is represented by the following Formula 6:

[0095] [ka]

[0096] In the above Chemical Formula 6, R and R 10 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and R9 is an alkylene group having 1 to 10 carbon atoms or -SiR 11 R 12 - and R 11 and R 12 are each independently an alkyl group having 1 to 10 carbon atoms, and PO may be an olefin polymer block.

[0097] According to one embodiment of the present invention, the organozinc compound may be prepared by a method including the steps of: preparing a Grignard reagent containing a styrene residue; and reacting the prepared Grignard reagent with a zinc compound to prepare the organozinc compound represented by Chemical Formula 5, and the zinc compound may be an alkylzinc alkoxide.

[0098] According to one embodiment of the present invention, the organozinc compound represented by Chemical Formula 5 prepared by the method for preparing an organozinc compound is synthesized as a single compound, does not contain side reaction products such as dimers, and does not contain chlorine-containing impurities that may act as catalyst poisons, such as organozinc chloride (R-Zn-Cl). Furthermore, when the organozinc compound represented by Chemical Formula 5 is prepared by the method for preparing an organozinc compound, it is synthesized as a single compound, which has the advantage of excellent synthesis reproducibility. Meanwhile, when preparing an organozinc compound, it is important to select a Grignard reagent containing a styrene residue and a zinc compound to avoid side reaction products and impurities, as in the present invention.

[0099] According to one embodiment of the present invention, the Grignard reagent containing a styrene residue may be represented by the following Chemical Formula 7:

[0100] [ka]

[0101] In the above formula 7, R and R 10 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and R9 is an alkylene group having 1 to 10 carbon atoms or -SiR 11 R 12 - and R 11 and R 12 are each independently an alkyl group having 1 to 10 carbon atoms, and X may be a halogen group.

[0102] According to one embodiment of the present invention, R and R 10 are each independently a single bond or an alkylene group having one carbon atom, and R9 is an alkylene group having one carbon atom or -SiR 11 R 12 - and R 11 and R 12 may each independently be an alkyl group having one carbon atom.

[0103] According to one embodiment of the present invention, the Grignard reagent containing a styrene residue represented by Chemical Formula 7 may be one selected from the group consisting of Grignard reagents containing a styrene residue represented by the following Chemical Formulas 7-1 to 7-4.

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] According to one embodiment of the present invention, the Grignard reagent containing a styrene residue represented by Formula 7 may be prepared by reacting a halide compound in which R8 is substituted with a halide (-X) with magnesium, specifically, magnesium powder or magnesium metal.

[0109] According to one embodiment of the present invention, the Grignard reagent containing a styrene residue represented by Chemical Formula 7 may be prepared by reacting a compound represented by the following Chemical Formula 8 with magnesium, specifically, magnesium powder or magnesium metal:

[0110] [ka]

[0111] In the above Chemical Formula 8, R and R 10are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and R9 is an alkylene group having 1 to 10 carbon atoms or -SiR 11 R 12 - and R 11 and R 12 are each independently an alkyl group having 1 to 10 carbon atoms, and X may be a halogen group.

[0112] According to one embodiment of the present invention, in Formula 8, R and R 10 are each independently a single bond or an alkylene group having 1 to 3 carbon atoms, and R9 is an alkylene group having 1 to 3 carbon atoms or -SiR 11 R 12 - and R 11 and R 12 are each independently an alkyl group having 1 to 3 carbon atoms, and X may be a halogen group.

[0113] According to one embodiment of the present invention, in Formula 8, R and R 10 are each independently a single bond or an alkylene group having one carbon atom, and R9 is an alkylene group having one carbon atom or -SiR 11 R 12 - and R 11 and R 12 are each independently an alkyl group having one carbon atom, and X may be one halogen group selected from the group consisting of Cl, Br, and I.

[0114] According to one embodiment of the present invention, the compound represented by Chemical Formula 8 may be one selected from the group consisting of compounds represented by the following Chemical Formulas 8-1 to 8-4.

[0115] [ka]

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] According to one embodiment of the present invention, when the Grignard reagent containing a styrene residue represented by Chemical Formula 7 is prepared, the reaction of the compound represented by Chemical Formula 8 with magnesium powder or magnesium metal may be carried out in an excess molar ratio, i.e., a molar ratio of more than 1 mole, of magnesium powder or magnesium metal per 1 mole of the compound represented by Chemical Formula 8. In this case, 50 mol % or more, 60 mol % or more, 70 mol % or more, 80 mol % or more, 90 mol % or more, 95 mol % or more, or 99 mol % or more of the compound represented by Chemical Formula 8 may be converted to the Grignard reagent containing a styrene residue represented by Chemical Formula 7.

[0120] According to one embodiment of the present invention, the reaction of the compound represented by Formula 8 with magnesium powder or magnesium metal may be carried out at a molar ratio of 1:1 to 10, 1:1 to 5, 1:1 to 2, or 1:1.01 to 1.60. Within these ranges, the conversion rate to the Grignard reagent containing a styrene residue represented by Formula 7 is high, the amount of magnesium remaining after the reaction is minimized, and the remaining magnesium powder or magnesium metal can be easily removed.

[0121] According to one embodiment of the present invention, the zinc compound must be a zinc compound that can be derived to substitute two organic groups of the same type on zinc when producing an organozinc compound. Zinc chloride (ZnCl) is often considered as a suitable zinc compound, but using zinc chloride as the zinc compound poses the problem of residual chlorine-containing impurities (e.g., alkylzinc chloride) that can act as a catalyst poison. Therefore, in the present invention, alkylzinc alkoxide is used as the zinc compound.

[0122] According to one embodiment of the present invention, the alkyl group of the alkyl zinc alkoxide may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or an ethyl group, and the alkoxide group may be an alkoxide group having 1 to 10 carbon atoms, an alkoxide group having 1 to 5 carbon atoms, an alkoxide group having 1 to 3 carbon atoms, or a methoxide group. As a specific example, the zinc compound may be ethyl zinc methoxide.

[0123] According to one embodiment of the present invention, the alkylzinc alkoxide may be prepared from dialkylzinc. Specifically, the alkylzinc alkoxide may be prepared by in situ reaction of dialkylzinc with an alcohol. In this case, the alkyl group of the dialkylzinc may be the same as the alkyl group of the alkylzinc alkoxide, and the alcohol may be an alcohol in which hydrogen is bonded to the alkoxide group of the alkylzinc alkoxide.

[0124] According to one embodiment of the present invention, when the alkyl zinc alkoxide is used as the zinc compound, a magnesium halide alkoxide is produced during the reaction of the Grignard reagent with the zinc compound. Since this is an insoluble salt, it is easy to filter and can prevent impurities from remaining.

[0125] According to one embodiment of the present invention, the reaction between the Grignard reagent and the zinc compound may be carried out at a molar ratio of 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, 1.5:1 to 1:1.5, or 1:1. When the molar ratio is within this range, the product is synthesized as a single compound, does not contain side reaction products such as dimers, does not contain impurities containing chlorine that can act as a catalyst poison, and can easily remove impurities containing magnesium that can act as a catalyst poison.

[0126] According to one embodiment of the present invention, all steps and all reactions of the method for preparing the zinc compound may be carried out in an organic solvent, and the reaction temperature and reaction pressure may be adjusted for the purpose of increasing the yield and purity.

[0127] In the method for preparing a zinc compound according to one embodiment of the present invention, conventional borane-based compounds containing styrene residues are replaced with Grignard reagents containing styrene residues, and alkyl zinc or zinc chloride is replaced with alkyl zinc alkoxide, thereby completely removing catalyst poisons.

[0128] According to one embodiment of the present invention, the catalyst composition may include an aluminoxane-based compound and a trialkylaluminum. As a specific example, the catalyst composition may include an aluminoxane-based compound and a trialkylaluminum represented by the following Chemical Formula 9. When the catalyst composition includes an aluminoxane-based compound and a trialkylaluminum, when a resin composition is produced from a block copolymer produced therefrom, the particle size and dispersity of the block copolymer can be adjusted, and the size of the domain regions and the distance between the multiple domain regions can be controlled.

[0129] According to one embodiment of the present invention, the aluminoxane-based compound represented by the following Formula 9 can function as a co-catalyst, a scavenger, or both a co-catalyst and a scavenger.

[0130] [Chemical formula 9] -[Al(R a )-O] m -

[0131] In the above chemical formula 9, R a are each independently a halogen radical; a hydrocarbyl radical having 1 to 20 carbon atoms; or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with a halogen, and m is an integer of 2 or greater.

[0132] According to one embodiment of the present invention, the compound represented by Chemical Formula 9 is not particularly limited as long as it is an alkylaluminoxane. Preferred examples include modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and a particularly preferred compound may be modified methylaluminoxane (MMAO).

[0133] According to one embodiment of the present invention, the compound represented by Formula 9 is an oligomeric compound produced by the reaction of alkylaluminum with water. When used as a co-catalyst, this reduces chain migration. This allows the production of high molecular weight copolymers and prevents the generation of homo-polyolefins as a side reaction. This ultimately allows the production of block copolymers that exhibit excellent physical properties, such as high tensile strength.

[0134] According to one embodiment of the present invention, the trialkylaluminum can serve as an additive for inducing alkyl exchange with an olefin polymer block intermediate during polymerization of the block copolymer and adjusting the structure of the block copolymer. Specifically, the trialkylaluminum may be a trialkylaluminum containing an alkyl group having 1 to 12 carbon atoms, and more specifically, a trialkylaluminum containing an alkyl group having 3 to 12 carbon atoms, 6 to 12 carbon atoms, 6 to 10 carbon atoms, or 6 to 8 carbon atoms. More specifically, the trialkylaluminum may be one or more selected from the group consisting of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-n-pentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum, and even more specifically, trioctylaluminum.

[0135] According to one embodiment of the present invention, the catalyst composition may contain an aluminoxane-based compound and a trialkylaluminum in a molar ratio of 1:0.01 to 10.0. Specific examples of the catalyst composition include an aluminoxane-based compound and a trialkylaluminum in a molar ratio of 1:0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, 0.05 or more, 0.06 or more, 0.07 or more, 0.08 or more, 0.09 or more, 0.1 or more, 0.2 or more, or 0.3 or more, or a molar ratio of 10.0 or less, 9.0 or less, 8.0 or less, 7.0 or less, 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, 2.0 or less, 1.0 or less, 0.9 or less, 0.8 or less, 0.7 or less, or 0.6 or less. Within these ranges, the weight-average molecular weight of the block copolymer and the molecular weight distribution can be controlled very broadly.

[0136] According to one embodiment of the present invention, when the transition metal compound represented by Chemical Formula 1, the aluminoxane compound represented by Chemical Formula 9, and trialkylaluminum are used in combination as the catalyst composition, a block copolymer satisfying the above-mentioned conditions can be prepared.

[0137] According to one embodiment of the present invention, the catalyst composition may include the transition metal compound represented by Chemical Formula 1, the aluminoxane compound represented by Chemical Formula 9, and trialkylaluminum supported on a carrier. The carrier may be, but is not limited to, silica or alumina.

[0138] According to one embodiment of the present invention, the catalyst composition may include a compound represented by the following Formula 10:

[0139] [Chemical formula 10] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0140] In the above Chemical Formula 10, Z is a Group 13 element, and each A is independently an aryl having 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, or an alkyl having 1 to 20 carbon atoms, and the substituent of A is a halogen, a hydrocarbyl having 1 to 20 carbon atoms, an alkoxy having 1 to 20 carbon atoms, or an aryloxy having 6 to 20 carbon atoms.

[0141] According to one embodiment of the present invention, step (S10) may be performed in a homogeneous solution state. In this case, a hydrocarbon solvent or the olefin monomer itself may be used as the solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents having 4 to 20 carbon atoms, specifically isobutane, hexane, cyclohexane, methylcyclohexane, etc. The solvent may be used alone or in combination of two or more.

[0142] According to one embodiment of the present invention, the polymerization temperature in step (S10) varies depending on the reactants, reaction conditions, etc., but may be specifically 70°C to 170°C, more specifically 80°C to 150°C, or 90°C to 120°C. When the temperature is within this range, the solubility of the polymer can be increased and the catalyst can be thermally stabilized.

[0143] According to one embodiment of the present invention, the polymerization in step (S10) may be carried out in a batch, semi-continuous, or continuous manner, and may also be carried out in two or more steps having different reaction conditions.

[0144] According to one embodiment of the present invention, the olefin polymer block intermediate prepared in step (S10) can serve as a precursor for preparing the block copolymer of the present invention through the polymerization reaction in step (S20) described below.

[0145] According to one embodiment of the present invention, the olefin-based monomer may be ethylene and an α-olefin-based monomer, and the α-olefin-based monomer is as described above in the block copolymer.

[0146] According to one embodiment of the present invention, step (S20) is a step of reacting an aromatic vinyl monomer with the olefin polymer block intermediate in the presence of a polymerization initiator to prepare a block copolymer.

[0147] According to one embodiment of the present invention, in step (S20), aromatic vinyl monomers are sequentially inserted between the zinc-carbon bonds of (polyolefinyl)2Zn contained in the olefin polymer block intermediate formed in step (S10), forming aromatic vinyl polymer block chains. Furthermore, styrene groups derived from the chain extender present at the end of the compound formed in step (S10) can participate as copolymerization sites with the aromatic vinyl monomers and be linked to the aromatic vinyl polymer block chains. Furthermore, the block copolymers produced through this process can be easily quenched by reacting the end groups with water, oxygen, or organic acids, thereby converting them into industrially useful polyolefin-polystyrene multiblock copolymers.

[0148] According to one embodiment of the present invention, the aromatic vinyl monomer is as described above in the block copolymer.

[0149] According to one embodiment of the present invention, the polymerization initiator may be an anionic polymerization initiator, and a specific example thereof may be an alkyllithium compound represented by the following Chemical Formula 11:

[0150] [ka]

[0151] In the above chemical formula 11, R 13 is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and Am is an amine compound represented by the following chemical formula 12: [ka] In the above chemical formula 12, R 14 ~R 18 are each independently hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and a and b are each independently an integer of 0 to 3, provided that a and b are not 0 at the same time.

[0152] According to one embodiment of the present invention, the R13 may be hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, or substituted or unsubstituted arylalkyl having 7 to 20 carbon atoms; 14 ~R 18 may each independently represent hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, or substituted or unsubstituted arylalkyl having 7 to 20 carbon atoms; a and b may each independently represent an integer of 0 to 2.

[0153] According to one embodiment of the present invention, the R 13 ~R 18 may each independently be hydrogen or alkyl having 1 to 20 carbon atoms; a may be 1 or 2, and b may be 0 or 1. Specifically, a may be an integer of 1 to 3, and b may be an integer of 0 to 3, more specifically, a may be 1 or 2, and b may be an integer of 0 to 2, and even more specifically, a may be 1 or 2, and b may be 0 or 1.

[0154] According to one embodiment of the present invention, Am in Formula 11 may be specifically represented by the following Formula 13 or 14.

[0155] [ka]

[0156] [ka]

[0157] In the above chemical formula, R 14 , R 15 , and R 18 are each independently hydrogen or alkyl having 1 to 20 carbon atoms.

[0158] According to an embodiment of the present invention, Am in Formula 11 may be specifically represented by the following Formula 13a or Formula 14a.

[0159] [ka]

[0160] [ka]

[0161] According to one embodiment of the present invention, the polymerization initiator represented by Formula 11 can be prepared by the following method: The method for preparing the polymerization initiator includes a step of adding and reacting a compound represented by Formula 16 and a compound represented by Formula 12 in the presence of a compound represented by Formula 15:

[0162] [ka]

[0163] [Chemical formula 15] B-Li

[0164] [ka]

[0165] In the above chemical formula, R 13 ~R 18 are each independently hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; a and b are each independently an integer of 0 to 3, provided that a and b are not both 0; and B is an alkyl having 1 to 20 carbon atoms.

[0166] According to one embodiment of the present invention, the R 13 may be hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; 14 ~R 18may each independently represent hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, or substituted or unsubstituted arylalkyl having 7 to 20 carbon atoms; a and b may each independently represent an integer of 0 to 2; and B may be alkyl having 1 to 12 carbon atoms.

[0167] According to one embodiment of the present invention, the R 14 ~R 18 are each independently hydrogen or alkyl having 1 to 20 carbon atoms; a may be an integer of 1 or 2, and b may be an integer of 0 or 1; and B may be alkyl having 1 to 8 carbon atoms. Specifically, a may be an integer of 1 to 3, and b may be an integer of 0 to 3, more specifically, a may be 1 or 2, and b may be an integer of 0 to 2, and even more specifically, a may be 1 or 2, and b may be 0 or 1.

[0168] According to one embodiment of the present invention, the alkyllithium compound represented by Formula 16 may be, for example, n-BuLi. n-BuLi is a substance widely used as an anionic polymerization initiator, and is easily available and has excellent cost efficiency.

[0169] According to one embodiment of the present invention, the method for preparing the polymerization initiator may be carried out by first reacting the compound represented by Chemical Formula 15 with the compound represented by Chemical Formula 16, and then reacting the compound represented by Chemical Formula 12 to prepare the compound represented by Chemical Formula 11. Specifically, by reacting the compound represented by Chemical Formula 15 with the compound represented by Chemical Formula 16, allyllithium is produced as an intermediate, and the allyllithium reacts with the compound represented by Chemical Formula 12 to finally form the polymerization initiator represented by Chemical Formula 11.

[0170] According to one embodiment of the present invention, the reaction of the compound represented by Formula 16 and the compound represented by Formula 12 in the presence of the compound represented by Formula 15 may be carried out in the absence of an additional solvent. The absence of an additional solvent means that, in the presence of the compound represented by Formula 16, other compounds that can serve as solvents are not present, or are present in trace amounts that do not significantly react with the compound represented by Formula 15, in addition to the compound represented by Formula 15 and the compound represented by Formula 12. When the reaction is carried out in the absence of an additional solvent, the reaction of the compound represented by Formula 15 with the compound represented by Formula 16 is the main reaction, and the polymerization initiator represented by Formula 11 can be effectively produced. The presence of another solvent is ineffective because it results in a mixture of the polymerization initiator represented by Formula 11, a compound produced by the reaction of the compound represented by Formula 15 with the compound represented by Formula 12, and a compound resulting from the decomposition of the compound produced by the reaction of the compound represented by Formula 15 with the compound represented by Formula 12.

[0171] According to one embodiment of the present invention, the polymerization initiator may be a silyl compound represented by the following Formula 17:

[0172] [ka]

[0173] In the above chemical formula 17, R 19 ~R 21 may each independently represent hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; R 22 may be a divalent alkylene group having 1 to 20 carbon atoms. 19 ~R 21 may each independently be a hydrocarbon group having 1 to 10 carbon atoms; R 22 may be a divalent alkylene group having 1 to 10 carbon atoms, and more specific examples include R 19 ~R 21 may each independently be a hydrocarbon group having 1 to 6 carbon atoms; R 22may be a divalent alkylene group having 1 to 6 carbon atoms. In the above Chemical Formula 17, Li may be R 22 The silyl compound represented by Formula 17 may be ionically bonded to the carbon located at the terminal of the alkylene group, thereby allowing the silyl compound represented by Formula 17 to function as an anionic polymerization initiator.

[0174] According to an embodiment of the present invention, the silyl compound represented by Formula 17 may be (trimethylsilyl)methyllithium. The silyl compound represented by Formula 17 may be mixed with the amine compound represented by Formula 12 to form a complex.

[0175] According to one embodiment of the present invention, in the step (S20), a polystyrene-based chain can be grown from the organozinc compound prepared in the step (S10), particularly, the polyolefin (polyolefinyl)2Zn in which an olefin-based polymer block chain is grown around zinc (Zn) by using the polymerization initiator as an initiator.

[0176] The present invention provides a resin composition.

[0177] According to one embodiment of the present invention, the resin composition may include a polyolefin resin and the block copolymer.

[0178] According to one embodiment of the present invention, the polyolefin resin forms a matrix region in the resin composition, and the block copolymer forms a domain region, so that the block copolymer of the domain region may be dispersed in the polyolefin resin of the matrix region.

[0179] According to one embodiment of the present invention, the resin composition may comprise 40 to 80% by weight of a polyolefin-based resin and 20 to 60% by weight of a block copolymer. Specifically, the resin composition may comprise 40% by weight or more, 41% by weight or more, 42% by weight or more, 43% by weight or more, 44% by weight or more, 45% by weight or more, 46% by weight or more, 47% by weight or more, 48% by weight or more, 49% by weight or more, or 50% by weight or more of the polyolefin-based resin, and 80% by weight or less, 79% by weight or less, 78% by weight or less, 77% by weight or less, 76% by weight or less, 75% by weight or less, 74% by weight or less, 73% by weight or less, 72% by weight or less, 71% by weight or less, or 70% by weight or less of the block copolymer, with the remainder being the block copolymer.

[0180] According to one embodiment of the present invention, the resin composition may contain the polyolefin resin and the block copolymer in a weight ratio of 1:0.11 to 1:9. Specific examples of the resin composition include the polyolefin resin and the block copolymer in a weight ratio of 1:0.11 to 4, 1:0.11 to 3, 1:0.11 to 2.4, 1:0.11 to 1.5, 1:0.11 to 1, 1:0.17 to 1.5, 1:0.17 to 1, or 1:0.17 to 0.25.

[0181] According to one embodiment of the present invention, when the resin composition contains a polyolefin-based resin and a block copolymer within the above ranges, the impact strength of the resin composition can be further improved, and a decrease in fluidity can be prevented, thereby improving processability.

[0182] According to one embodiment of the present invention, the polyolefin resin may be polypropylene. Specifically, the polypropylene may be a polypropylene homopolymer or a copolymer of propylene and an α-olefin monomer, and in this case, the copolymer may be an alternating, random, or block copolymer.

[0183] According to one embodiment of the present invention, the α-olefin monomer in the polypropylene may be specifically an aliphatic olefin having 2 to 12 carbon atoms or 2 to 8 carbon atoms. More specifically, examples thereof include ethylene, 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-itocene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, and 3,4-dimethyl-1-hexene, and any one or a mixture of two or more thereof may be used.

[0184] According to one embodiment of the present invention, the polypropylene may be any one or a mixture of two or more selected from the group consisting of polypropylene homopolymer, propylene-α-olefin copolymer, and propylene-ethylene-α-olefin copolymer, and the copolymer may be a random or block copolymer.

[0185] According to one embodiment of the present invention, the polypropylene has a melt index (MI) of 0.5 g / 10 min to 100 g / 10 min, measured according to ASTM D1238 at 230°C under a load of 2.16 kg, and may be 0.5 g / 10 min to 1.0 g / 10 min, or 2.0 g / 10 min or more, and 100 g / 10 min to 90 g / 10 min, or 50 g / 10 min to 50 g / 10 min. When the MI is within this range, the processability of the resin composition during injection molding can be further improved. Furthermore, the polypropylene is a copolymer having the above melt index, and specific examples thereof include propylene-ethylene copolymers or high-crystalline polypropylene (HCPP), which can further improve strength properties.

[0186] According to one embodiment of the present invention, the polypropylene may have a DSC melting point of 120°C or more and 160°C or less.

[0187] According to one embodiment of the present invention, the polypropylene may be prepared using a conventional polymer preparation reaction to satisfy the above physical property requirements, or may be commercially available. TM M1600 from Korea Petrochemical Co., Ltd., CB5230 from Korea Petrochemical Co., Ltd., etc. The polypropylene may also be a random propylene copolymer, such as Braskem America Inc.'s Braskem TM PP R7021-50RNA or Formolene from Formosa Plastics Corporation, USA TM It may be 7320A or the like.

[0188] According to one embodiment of the present invention, the resin composition may optionally further contain an inorganic filler to improve the mechanical properties of the resin composition. The inorganic filler may be a powdered filler, a flake filler, a fibrous filler, or a bulge filler, and a mixture of any one or more of these may be used. Specific examples of the powdered filler include natural silicic acid or silicates such as finely powdered talc, kaolinite, plastic clay, and sericite; carbonates such as precipitated calcium carbonate, ground calcium carbonate, and magnesium carbonate; hydroxides such as aluminum hydroxide and magnesium hydroxide; oxides such as zinc oxide, magnesium oxide, and titanium oxide; synthetic silicic acid or silicates such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, and silicic anhydride; and silicon carbide. Examples of the flake filler include mica. Examples of the fibrous filler include basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fiber), and potassium titanate. Examples of the balloon-shaped filler include glass balloons. Among these, talc is preferred.

[0189] According to one embodiment of the present invention, the inorganic filler may be surface-treated to improve the strength and moldability of the resin composition. Specifically, the inorganic filler may be physically or chemically surface-treated using a surface treatment agent such as a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, a resin acid, or polyethylene glycol.

[0190] According to one embodiment of the present invention, the inorganic filler has an average particle size (D 50 The average particle size (D) of the inorganic filler may be 1 μm to 20 μm, specifically 3 μm to 15 μm, and more specifically 5 μm to 10 μm. When it is within this range, it is possible to uniformly disperse it in the resin composition, and the mechanical properties can be further improved. 50 ) can be defined as the particle size at 50% of the volume particle size distribution. In the present invention, the average particle size (D 50 ) can be measured, for example, by observation with an electron microscope using a scanning electron microscope (SEM) or a field emission scanning electron microscope (FE-SEM), or by the laser diffraction method. When measuring by the laser diffraction method, more specifically, the inorganic filler particles are dispersed in a dispersion medium, and then introduced into a commercially available laser diffraction particle size measuring device (e.g., Microtrac MT 3000), and the average particle size (D) at 50% of the volume particle size distribution measured by the measuring device is measured. 50 ) can be calculated.

[0191] According to one embodiment of the present invention, the inorganic filler may be included in an amount of 0.1 to 40 parts by weight, or 0.1 to 20 parts by weight, based on 100 parts by weight of the total content of the polyolefin resin and the block copolymer. When the amount is within this range, deterioration in processability can be prevented and mechanical properties can be further improved.

[0192] According to one embodiment of the present invention, the resin composition may be prepared by adding a polyolefin resin and optionally an inorganic filler to a block copolymer, mixing the mixture, and then heat treating the mixture. The mixing process may be performed by a conventional method. Specifically, the mixing may be performed using a supermixer or a ribbon mixer.

[0193] According to an embodiment of the present invention, additives such as an antioxidant, a heat stabilizer, a UV stabilizer, an antistatic agent, etc. may be further added during the mixing, if necessary. In order to improve coatability, a small amount of an adhesive resin or an additive having a polar group may be selectively added within an appropriate content range.

[0194] According to one embodiment of the present invention, the heat treatment may be performed at a temperature equal to or higher than the melting point of the polyolefin resin and equal to or lower than 210° C. The heat treatment process may be performed using various compounding machines such as a conventional twin-screw extruder, a single-screw extruder, a roll mill, a kneader, or a Banbury mixer.

[0195] According to one embodiment of the present invention, the resin composition is useful for blow molding, extrusion molding, or injection molding in various fields and applications, such as materials for automobiles, electric wires, toys, fibers, medical products, various packaging applications, construction applications, and daily necessities. In particular, the resin composition has excellent toughness and impact strength at both room temperature and low temperature, as well as excellent physical properties such as heat resistance and rigidity, and therefore can be useful for interior and exterior parts of automobiles.

[0196] According to one embodiment of the present invention, the resin composition may have an impact strength of 5.0 kgf·m / m or more at −50° C. as measured by ADTM D 256. Specific examples of the resin composition may have an impact strength of 5.0 kgf·m / m or more, 5.1 kgf·m / m or more, 5.2 kgf·m / m or more, 5.3 kgf·m / m or more, 5.4 kgf·m / m or more, 5.5 kgf·m / m or more, 5.6 kgf·m / m or more, 5.7 kgf·m / m or more, or 5.8 kgf·m / m or more as measured by ADTM D 256, and may have an impact strength of 20.0 kgf·m / m or less, 15.0 kgf·m / m or less, 10.0 kgf·m / m or less, 9.5 kgf·m / m or less, or 9.1 kgf·m / m or less.

[0197] According to one embodiment of the present invention, the resin composition is used to produce a cast film having a thickness of 80 μm and a width of 25.4 mm on a monolayer cast film line having a melting temperature of 230°C and a cooling roll temperature of 25°C. The seal strength of the produced film is measured at 90°C and 100°C under the following conditions using a J&B Universal Sealing Machine Type 5000MB. When the seal initiation temperature at which the seal strength reaches 3 N is calculated by linear interpolation from the seal strengths at 90°C and 100°C, the seal strength at 90°C may be 0.80 N or more, the seal strength at 100°C may be 4.50 N or more, and the seal initiation temperature may be 96.0°C or less. -Sealing pressure: 0.1N / mm 2 -Sealing time: 0.1 seconds -Cooling time: 99 seconds - Peeling speed: 10mm / sec -Starting temperature: 80℃ -End temperature: 150℃ -Temperature increase: 10℃

[0198] According to one embodiment of the present invention, the resin composition may have a seal strength of 0.80 N or more at 90°C. Specific examples include 0.81 N or more, 0.82 N or more, 0.83 N or more, 0.84 N or more, or 0.85 N or more, and 1.5 N or less, 1.4 N or less, 1.3 N or less, 1.2 N or less, 1.1 N or less, or 1.08 N or less.

[0199] According to one embodiment of the present invention, the resin composition may have a seal strength of 4.50 N or more at 100°C. Specific examples include 4.55 N or more, 4.60 N or more, 4.65 N or more, 4.70 N or more, 4.75 N or more, 4.80 N or more, 4.85 N or more, 4.90 N or more, 4.95 N or more, or 4.96 N or more, and may have a seal strength of 10.0 N or less, 9.0 N or less, 8.0 N or less, 7.0 N or less, 6.0 N or less, or 5.85 N or less.

[0200] According to one embodiment of the present invention, the resin composition may have a sealing initiation temperature of 96.0° C. or less. Specific examples include 95.9° C. or less, 95.8° C. or less, 95.7° C. or less, 95.6° C. or less, 95.5° C. or less, 95.4° C. or less, 95.3° C. or less, or 95.2° C. or less, or 90.0° C. or more, 91.0° C. or more, 92.0° C. or more, 93.0° C. or more, or 94.0° C. or more.

[0201] Although the present invention may be embodied in various different forms, it is not intended to be limited to the embodiments set forth herein, and the present invention is not limited to the embodiments set forth herein.

[0202] Reagents and experimental conditions All experiments were performed under an inert atmosphere using standard glovebox and Schlenk techniques. Toluene, hexane, and tetrahydrofuran (THF) were distilled using benzophenone ketyl. Anhydrous-grade methylcyclohexane used in the polymerization reactions was purchased from Tokyo Chemical Industry (TCI) and purified using Na / K alloy. Sublimation-grade HfCl4 was purchased from Streme and used as received. Ethylene-propylene gas mixtures were purified using trioctylaluminum (0.6 M in mineral spirits) in a bomb reactor (2.0 L). 1 H NMR (600 MHz) and 13 C NMR (150 MHz) spectra were recorded using an ECZ 600 instrument (JEOL).

[0203] GPC data were analyzed in 1,2,4-trichlorobenzene at 160°C using a PL-GPC220 system equipped with a refractive index detector and two columns (PLarian Mixed-B 7.5 x 300 mm Varian [Polymer Lab]).

[0204] (1) Preparation of transition metal compound represented by chemical formula 1-1 [ka]

[0205] 1) Preparation of ligand compounds [ka] 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. The mixture was heated to 70 °C overnight with stirring. After filtration, the solvent was removed on a rotary evaporator to give a yellow solid (1.07 g, 84%). 1 H NMR(C6D6): 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(C6D6): 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 + ] C 24 H 29 BrN2) 424.1514. Found: 424.1516.

[0206] Under nitrogen, a Schlenk flask was charged with the above compound (1.07 g, 2.51 mmol), 1-naphthylboronic acid (0.453 g, 2.64 mmol), NaCO (0.700 g, 6.60 mmol), and toluene (5 mL). A solution of (PhP)Pd (7.83 mg, 0.00678 mmol) in degassed HO / EtOH (1 mL, v / v, 1:1) and toluene (1 mL) was added. Column chromatography on silica gel using hexane and ethyl acetate (v / v, 90:3:1) containing a small amount of triethylamine afforded a pale yellow oil (0.712 g, 60%). 1H NMR(C6D6): 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(C6D6): 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 + ] C 34 H 36 N2) 472.2878. Found: 472.2878.

[0207] 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, ammonium chloride (0.30 g) in water (10 mL) was added, and the product was extracted with diethyl ether (3 x 10 mL). The resulting oil was dried overnight under high vacuum at 60 °C. A yellow solid was obtained (0.257 g, 83%). 1H NMR(C6D6): 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, CH3), 1.00(m, 1H), 0.980(d, J = 6.6 Hz, 3H, CH3), 0.921(m, 3H) ppm. 13 C NMR(C6D6): δ 23.78, 24.45, 26.63, 27.42, 27.54, 28.96, 34.77, 35.08, 39.01, 67.64, 119.99, 122.89, 124.13, 124.80, 125.36, 125.77, 126.08, 126.46, 126.56, 126.71, 127.58, 128.55, 129.35, 131.84, 134.64, 136.94, 138.77, 141.88, 142.24, 144.97, 146.32, 159.28, 163.74 ppm. HRMS(EI): m / z calcd([M + C 43 H 48 N2) 592.3817. Found: 592.3819.

[0208] 2) Manufacturing of migrating metal compounds A Schlenk flask was charged with the prepared ligand compound (0.150 g, 0.253 mmol) in toluene (1.5 g), and n-BuLi (0.17 mL, 1.6 M solution in hexane, 0.27 mmol) was added dropwise at room temperature. After stirring for 1 hour, HfCl4 (0.0814 g, 0.254 mmol) was added as a solid. The reaction mixture was heated to 100 °C and stirred for 2 hours. After cooling, MeMgBr (0.29 mL, 3.1 M solution in diethyl ether, 0.89 mmol) was added and stirred at room temperature overnight. After removing the volatiles using a vacuum line, the product was extracted with toluene (1.5 g). The extract was filtered through Celite. After removing the solvent using a vacuum line, the residue was softened with hexane (2 mL) to give a yellow solid (0.128 g, 63%). 1 H NMR(C6D6): 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, CH3), 1.07(m, 3H), 0.99(s, 3H, HfCH3), 0.95(m, 2H), 0.73(d, J= 7.2 Hz, 3H, CH3), 0.70(s, 3H, HfCH3), 0.23(m, 1H) ppm. 13 C NMR(C6D6): 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. Anal. calcd.(C 45 H 52 HfN2): C, 67.61; H, 6.56; N, 3.50%. Found: C, 67.98; H, 6.88; N, 3.19%.

[0209] (2) Manufacturing of organic lead compounds To 78 mL of diethyl ether, 15.0 g (98.3 mmol) of 4-vinylbenzyl chloride and 2.628 g (108.1 mmol) of magnesium metal were added. The mixture was stirred at 0°C for 1.0 hour and then filtered through Celite to remove excess magnesium. 19.2 g (81.9 mmol) of p-tosyl-OCH2CH2Cl dissolved in 27 mL of diethyl ether was added dropwise to the 4-vinylbenzyl-magnesium chloride (4-vinylbenzyl-MgCl) Grignard reagent prepared above. After stirring overnight, the mixture was filtered through Celite to remove the insoluble salt magnesium chloride tosylate (MgCl(OTs)). The filter cake was washed three times with 70 mL of hexane, and the solvent was removed using a rotary evaporator to obtain 14.2 g of crude product. 43 mg (3,000 ppm) of t-butylcatechol was added as a radical scavenger, and the mixture was distilled under complete vacuum at 85°C to obtain a compound represented by the following chemical formula 8-4-1. The weight of the obtained compound was measured, and the yield was 81% by weight (12.0 g). 1 H NMR and 13 C NMR spectra were measured.

[0210] [ka] 1 H NMR(C6D6): 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, =CH2), 5.09 (d, J = 9.6 Hz, 1H, =CH2), 3.04 (t, J = 6.6 Hz, 2H, CH2), 2.42 (t, J = 6.6 Hz, 2H, CH2), 1.64 (quintet, J = 6.6 Hz, 2H, CH2Cl) ppm. 13C NMR(C6D6): δ 32.61, 34.12, 44.07, 113.13, 126.74, 128.97, 135.99, 137.11, 140.63 ppm.

[0211] Next, 10.0 g (55.3 mmol) of the compound represented by formula 8-4-1 (4-(3-chloropropyl)styrene) prepared above was dissolved in a mixed solvent of 20 mL of toluene and 7.98 g (111 mmol) of tetrahydrofuran (THF). This was then added dropwise to a stirred 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, when slight heat was gradually generated, the reaction mixture was filtered through Celite to remove excess magnesium. 6.94 g (55.3 mmol, 1 equivalent relative to the Grignard reagent) of ethylzinc methoxide (EtZn(OMe)), generated by the in situ reaction of 6.83 g (55.3 mmol) of diethylzinc (EtZn) and 1.78 g (55.3 mmol) of methanol in 30 mL of toluene at room temperature for 1.0 hour, was added to the filtrate. Next, 60 ml of toluene was added, and the mixture was stirred at room temperature for 1.0 hour. The solvent was then removed using a high vacuum line. 96 g of hexane was then added, and the insoluble salt magnesium chloride methoxide (MgCl(OMe)) was removed on Celite. The filtrate was stored at -30°C, and the compound represented by formula 5-4 was evaporated as a white crystalline solid. The weight was measured, and the yield was 56 wt% (7.28 g). 1 H NMR and 13 C NMR spectra were measured.

[0212] [ka] 1H NMR(C6D6): 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, =CH2), 5.11 (d, J = 11 Hz, 1H, =CH2), 2.43 (t, J = 7.2 Hz, 2H, CH2), 1.80 (quintet, J = 7.2 Hz, 2H, CH2), -0.19 (t, J = 7.2 Hz, 2H, CH2Zn) ppm. 13 C NMR(C6D6): δ 12.66, 28.82, 40.09, 113.15, 127.31, 129.23, 136.05, 137.10, 142.91 ppm.

[0213] (3) Production of anionic polymerization initiators (Trimethylsilyl)methyllithium (3,100 μmol, 291.9 mg) and N,N,N',N",N"-pentamethyldiethylenetriamine (3,100 μmol, 537.2 mg) were mixed with methylcyclohexane (20.7 g) and stirred at room temperature for 30 minutes to prepare an anionic polymerization initiator.

[0214] Example Example 1 <Production of Block Copolymer> A Parr reactor (3.785 L) was vacuum dried for 2 hours at 120° C. A solution of MMAO (600 mg, 1,000 μmol Al) as a scavenger and trioctylaluminum (183.3 mg, 500 μmol) as an additive in methylcyclohexane (1,200 g) was charged into the reactor, and the mixture was stirred at 120° C. for 1 hour using a heating jacket, and then the solution was removed using a cannula.

[0215] The reactor was charged with methylcyclohexane (1,200 g) containing MMAO (1,000 μmol-Al) and trioctylaluminum (500 μmol) as scavengers, 1-hexene (880 g) as an α-olefin monomer, and the temperature was set to 90° C. A solution of the organozinc compound (4,200 μmol) in methylcyclohexane (5 g) was charged as a chain transfer agent, followed by the addition of [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] - A methylcyclohexane solution containing the transition metal compound (10 μmol-Hf) activated with (1.0 eq) was poured into the reactor. The valve of the ethylene tank was opened, and polymerization was carried out for 40 minutes at a temperature range of 90°C to 120°C while maintaining the pressure inside the reactor at 25 bar. After polymerization, the ethylene gas was discharged, and the temperature of the reactor was further adjusted to 90°C.

[0216] When the temperature reached 90°C, the anionic polymerization initiator (3,100 μmol) prepared above was added. The temperature was maintained at 90°C for 30 minutes with stirring, and then styrene (52 g) was added. The temperature was adjusted to the range of 90°C to 100°C using a heating jacket. The viscosity gradually increased and reached a nearly invisible state within 5 hours. 1 An aliquot was taken for analysis by H NMR spectroscopy. 1 H NMR analysis confirmed the complete conversion of styrene. After the 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 to obtain the block copolymer.

[0217] <Production of Resin Composition> To 40 parts by weight of the block copolymer prepared above, 60 parts by weight of terpolymer polypropylene (RANPELEN SFC750D, manufactured by Lotte Chemical Co., Ltd.) with a melt index (230°C, 2.16 kg) of 7 g / 10 min was added, and then the mixture was solution-blended in xylene using a reactor to prepare a resin composition compound. The blending was carried out at a temperature of 200°C to 230°C, with an impeller rotation speed of 400 rpm, and for a blending time of 4 hours. After blending was completed, the compound was recovered and dried overnight in a vacuum oven at 100°C to obtain a resin composition.

[0218] Examples 2 and 3 A block copolymer and a resin composition were obtained in the same manner as in Example 1, except that the types and contents of the transition metal compound, scavenger, organozinc compound, α-olefin monomer, styrene, polymerization initiator, and additives were changed as shown in Table 1 below.

[0219] Comparative Example 1 A resin composition was obtained in the same manner as in Example 1, except that, in producing the resin composition, G1645 manufactured by Kraton, a commercially available styrene-ethylene-butylene-styrene block copolymer (SEBS), was used instead of the block copolymer produced in Example 1.

[0220] Comparative Examples 2 to 6 A block copolymer and a resin composition were obtained in the same manner as in Example 1, except that the types and contents of the transition metal compound, scavenger, organozinc compound, α-olefin monomer, styrene, polymerization initiator, and additives were changed as shown in Table 1 below.

[0221] [Table 1]

[0222] Experimental example Experimental Example 1 The content of each monomer unit, weight average molecular weight, and molecular weight distribution of the block copolymers prepared in Examples 1 to 3 and Comparative Examples 2 to 6 and the block copolymer of Comparative Example 1 were measured by the following methods, and the results are shown in Table 2 below.

[0223] *Ethylene, α-olefin, and styrene contents (wt%) were measured by NMR. Specifically, they were measured using a Bruker 600MHz AVANCE III HD NMR device. 1 H NMR was measured under conditions of ns = 16, dl = 3 s, solvent = TCE-d2, 373 K, and the TCE-d2 solvent peak was corrected to 6.0 ppm. The CH3 of 1-propylene was confirmed at 1 ppm, and the CH3-related peak (triplet) of butyl branched 1-hexene was confirmed at around 0.96 ppm, and the content was calculated after confirming it. The styrene content was also calculated from the aromatic peaks around 6.5-7.5 ppm.

[0224] *Weight-average molecular weight (Mw, g / mol) and molecular weight distribution (polydispersity index, PDI): Weight-average molecular weight (Mw, g / mol) and number-average molecular weight (Mn, g / mol) were measured using gel permeation chromatography (GPC), and the molecular weight distribution (polydispersity index, PDI) was calculated by dividing the weight-average molecular weight by the number-average molecular weight.

[0225] -Column: PL Olexis -Solvent: TCB (trichlorobenzene) -Flow rate: 1.0ml / min -Sample concentration: 1.0mg / ml -Injection volume: 200μl -Column temperature: 160℃ -Detector:Agilent High Temperature RI detector -Standard: Polystyrene - Using the Mark-Houwink formula (K=40.8X10 -5 , α=0.7057), molecular weight calculated by Universal Calibration

[0226] [Table 2]

[0227] As shown in Table 2, it was confirmed that the block copolymers prepared in Examples 1 to 3 exhibited the weight average molecular weight and molecular weight distribution defined in the present invention.

[0228] In contrast, the block copolymer of Comparative Example 1 had a very low weight average molecular weight, and it was confirmed that the molecular weight distribution was significantly narrower than the molecular weight distribution limited by the present invention.

[0229] In addition, in Comparative Example 2, in which the same α-olefin monomer, 1-hexene, as in Example 1 was added, it was confirmed that even though the same amounts of catalyst, scavenger, polymerization initiator, and additives were added, the molecular weight distribution was narrower than the molecular weight distribution defined in the present invention due to the changes in the amounts of α-olefin monomer, styrene, and organozinc compound.

[0230] In addition, in Comparative Example 3, in which the same α-olefin monomer as in Example 1, 1-hexene, was used, the contents of the catalyst, organozinc compound, initiator, α-olefin monomer, and styrene, excluding the scavenger, were changed, and in particular, since no additives were used, it was confirmed that not only was the molecular weight distribution narrower than the molecular weight distribution defined in the present invention, but also the weight average molecular weight was low.

[0231] In addition, in Comparative Example 4, in which the same α-olefin monomer, 1-octene, as in Example 2 was added, the same amounts of scavenger, organozinc compound, and initiator were added, but the contents of catalyst, α-olefin monomer, and styrene were different. In particular, because no additives were added, even though the contents of ethylene monomer units, α-olefin-based monomer units, and styrene monomer units were adjusted similarly to Example 2, it was confirmed that the molecular weight distribution was narrower than the molecular weight distribution defined in the present invention.

[0232] In addition, in Comparative Example 5, in which the same α-olefin monomer, 1-butene, as in Example 3 was added, the same amounts of scavenger and organozinc compound were added, but the contents of catalyst, initiator, α-olefin monomer, and styrene were different. In particular, because no additive was added, it was confirmed that the weight average molecular weight was significantly low even though the contents of ethylene monomer units, α-olefin-based monomer units, and styrene monomer units were adjusted similarly to Example 3.

[0233] In addition, in Comparative Example 6, in which the same α-olefin monomer, 1-hexene, as in Example 1 was added, the contents of the catalyst, organozinc compound, initiator, α-olefin monomer, and styrene, excluding the scavenger, were changed, and it was confirmed that the weight average molecular weight increased, particularly because no additives were added.

[0234] Experimental Example 2 The low-temperature impact strength, seal strength, and seal initiation temperature of the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 6 were measured by the following methods, and the results are shown in Table 3 below.

[0235] *Low-temperature impact strength (kgf·m / m): Each resin composition prepared in the examples and comparative examples was injected into a 210°C mold at 6 bar pressure for 10 seconds and molded into a notched specimen measuring 63.5 mm x 12.5 mm x 3.2 mm in accordance with ASTM D256. The notch length of the prepared specimen was 5 mm. The Charpy impact strength at low temperature (-50°C) was measured using a Tinius Olsen Model IT 504 Impact Tester with two pendulums (2025) in accordance with ASTM D256. The low-temperature (-50°C) impact strength was measured by placing the prepared specimen in a low-temperature chamber set at -50°C and exposing it to -50°C for at least 12 hours. The impact strength was measured within 3 seconds of removing it from the low-temperature chamber.

[0236] *Low temperature seal strength (N) and seal initiation temperature (°C): Using the resin compositions produced in the above examples and comparative examples, cast films with a thickness of 80 μm and a width of 25.4 mm were produced on a single-layer cast film line with a melting temperature of 230°C and a cooling roll temperature of 25°C. Using the produced films, the seal strengths at 90°C and 100°C were measured under the following conditions using a J&B Universal Sealing Machine Type 5000MB, and the seal initiation temperature at which the seal strength reached 3N was calculated by linear interpolation from the seal strengths at 90°C and 100°C. -Sealing pressure: 0.1N / mm 2 -Sealing time: 0.1 seconds -Cooling time: 99 seconds - Peeling speed: 10mm / sec -Starting temperature: 80℃ -End temperature: 150℃ -Temperature increase: 10℃

[0237] [Table 3]

[0238] As shown in Table 3, the resin compositions prepared using the block copolymers prepared in Examples 1 to 3 of the present invention were found to have significantly improved low-temperature impact strength, low-temperature seal strength, and seal initiation temperature compared to the resin composition of Comparative Example 1 prepared using Kraton G1645, a commercially available styrene-ethylene-butylene-styrene block copolymer (SEBS), as the block copolymer.

[0239] In contrast, it was confirmed that the resin composition prepared using the block copolymer prepared in Comparative Example 2 showed only a very small improvement in low-temperature impact strength compared to the resin composition prepared using the block copolymer of Example 1, which contains the same α-olefin monomer units.

[0240] Furthermore, it was confirmed that the resin composition prepared using the block copolymer prepared in Comparative Example 3 had lower low-temperature seal strength and higher seal initiation temperature than the resin composition prepared using the block copolymer of Example 1, which contains the same α-olefin monomer units. The fact that Comparative Example 3 exhibited higher low-temperature impact strength despite having a narrower molecular weight distribution than Comparative Example 2 is believed to be due to the monomer composition.

[0241] Furthermore, it was confirmed that the resin composition prepared using the block copolymer prepared in Comparative Example 4 had significantly lower low-temperature sealing strength and higher sealing initiation temperature than the resin composition prepared using the block copolymer of Example 2, which contains the same α-olefin monomer units.

[0242] Furthermore, it was confirmed that the resin composition prepared using the block copolymer prepared in Comparative Example 5 had significantly lower low-temperature seal strength and higher seal initiation temperature than the resin composition prepared using the block copolymer of Example 3, which contains the same α-olefin monomer units.

[0243] Furthermore, the resin composition prepared including the block copolymer prepared in Comparative Example 6 showed increased low-temperature impact strength and low-temperature seal strength as the weight-average molecular weight of the block copolymer increased, compared to the resin composition prepared including the block copolymer of Example 1 containing the same α-olefin monomer units, but the seal initiation temperature was very high, indicating that the seal initiation temperature was not improved.

[0244] These results confirm that the weight-average molecular weight and molecular weight distribution of the block copolymer defined in the present invention can improve the low-temperature seal strength, seal initiation temperature, and low-temperature impact strength of the resin composition, and therefore the polyolefin resin composition of the present invention is particularly suitable as a medical material.

[0245] Furthermore, it was confirmed that when a block copolymer is produced by the method for producing a block copolymer of the present invention, a block copolymer having a wide molecular weight distribution can be produced in accordance with the object of the present invention.

Claims

1. The copolymer comprises an aromatic vinyl polymer block and an olefin polymer block, The weight average molecular weight (Mw) is 110,000 g / mol or more and 200,000 g / mol or less, A block copolymer having a molecular weight distribution (Mw / Mn) of 2.4 or more and 2.9 or less.

2. The block copolymer according to claim 1 , wherein the olefin polymer block comprises ethylene monomer units and α-olefin monomer units.

3. 2. The block copolymer according to claim 1, wherein the olefin polymer block comprises an ethylene monomer unit and an α-olefin monomer unit having 3 to 20 carbon atoms.

4. The block copolymer according to claim 2, wherein the α-olefin monomer is at least one selected from the group consisting of 1-propene, 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, and 3,4-dimethyl-1-hexene.

5. 2. The block copolymer according to claim 1, comprising 10% by weight or more and 20% by weight or less of an aromatic vinyl polymer block and 80% by weight or more and 90% by weight or less of an olefin polymer block.

6. 2. The block copolymer according to claim 1, comprising 45% by weight or more and 55% by weight or less of α-olefin monomer units having 3 to 20 carbon atoms.

7. The block copolymer according to claim 1 , which contains 25% by weight or more and 45% by weight or less of ethylene monomer units.

8. The block copolymer according to claim 1 , which does not contain any unsaturated double bonds.

9. (S10) a step of polymerizing one or more olefin monomers in the presence of a chain transfer agent using a catalyst composition including a transition metal catalyst, an aluminoxane compound, and a trialkylaluminum to prepare an olefin polymer block intermediate; and (S20) adding a polymerization initiator and an aromatic vinyl monomer in the presence of the olefin polymer block intermediate produced in the (S10) step, and polymerizing the monomer to produce a block copolymer.

10. The method for producing a block copolymer according to claim 9, wherein the trialkylaluminum is trioctylaluminum.

11. The method for producing a block copolymer according to claim 9 , wherein the catalyst composition contains an aluminoxane compound and a trialkylaluminum in a molar ratio of 1:0.01 or more and 10.0 or less.

12. A resin composition comprising a polyolefin resin and the block copolymer according to claim 1 .

13. The resin composition according to claim 12, comprising 40% by weight or more and 80% by weight or less of a polyolefin resin and 20% by weight or more and 60% by weight or less of a block copolymer.

14. The resin composition according to claim 12, having an impact strength of 5.0 kgf·m / m or more at −50° C. as measured by ADTM D256.

15. The resin composition according to claim 12, wherein the seal strength at 90°C measured under the following conditions using a J&B Universal Sealing Machine Type 5000MB using a film having a thickness of 80 µm and a width of 25.4 mm is 0.80 N or more. - Sealing pressure: 0.1 N / mm ２ - Sealing time: 0.1 seconds - Cooling time: 99 seconds Peeling speed: 10 mm / sec - Starting temperature: 80℃ -End temperature: 150℃ - Temperature increase: 10°C

16. The resin composition according to claim 12, wherein the seal strength at 100°C measured under the following conditions using a J&B Universal Sealing Machine Type 5000MB using a film having a thickness of 80 µm and a width of 25.4 mm is 4.50 N or more. - Sealing pressure: 0.1 N / mm ２ - Sealing time: 0.1 seconds - Cooling time: 99 seconds Peeling speed: 10 mm / sec - Starting temperature: 80℃ -End temperature: 150℃ - Temperature increase: 10°C

17. 13. The resin composition according to claim 12, wherein the sealing initiation temperature at which the seal strength reaches 3N is calculated by linear interpolation from the seal strengths measured at 90°C and 100°C under the following conditions using a film having a thickness of 80 μm and a width of 25.4 mm using a J&B Universal Sealing Machine Type 5000MB, is 96.0°C or less. - Sealing pressure: 0.1 N / mm ２ - Sealing time: 0.1 seconds - Cooling time: 99 seconds Peeling speed: 10 mm / sec - Starting temperature: 80℃ -End temperature: 150℃ - Temperature increase: 10°C

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