Thermoplastic resin composition

Abstract

The present invention relates to a thermoplastic resin composition comprising a polyolefin-polystyrene multi-block copolymer having a structure in which a polystyrene chain is connected to both ends of a polypropylene chain and a polyolefin chain, and the thermoplastic resin composition of the present invention has significantly improved low-temperature and room-temperature impact strength properties and high fluidity, and thus can exhibit excellent molding processability.

Description

Technical Field

[0001] This application claims the benefit of Korean Patent Application No. 10-2020-0095282, filed on July 30, 2020, and Korean Patent Application No. 10-2021-0100046, filed on July 29, 2021, in the Korean Intellectual Property Office, the disclosures of which are incorporated herein by reference in their entirety.

[0002] The present invention relates to a thermoplastic resin composition comprising a polyolefin-polystyrene-based multi-block copolymer having a structure in which a polystyrene chain is connected to both ends of a polypropylene chain and a polyolefin chain. Background Art

[0003] Polypropylene has excellent rigidity and molding processability, and is therefore widely used as a material for automotive interior and exterior trims, but it has weak impact strength, which is disadvantageous. Therefore, as a composition for automotive interior and exterior trims, a polypropylene-based resin composition containing polypropylene (PP) as a main component, an impact-resistant reinforcing material, and an inorganic filler is generally used.

[0004] Usually, as the material of automobile interior and exterior decoration, particularly the material of bumper cover, ethylene propylene rubber (EPR) or ethylene propylene diene rubber (EPDM) are mainly used as the impact resistance reinforcement material in most polypropylene resin compositions. Due to the introduction of ethylene-alpha-olefin copolymer synthesized by metallocene catalyst, the ethylene-alpha-olefin copolymer has been used as the impact resistance reinforcement material. The polypropylene resin composition using ethylene-alpha-olefin copolymer has the physical properties such as balanced impact strength, elastic modulus, bending rigidity, has good formability, and is cheap. However, the polypropylene resin composition utilizing ethylene-alpha-olefin copolymer depends on various use environments to ensure that there is limitation in terms of impact resistance.

[0005] In addition, styrene-ethylene-butylene-styrene (SEBS), which is a styrene-based thermoplastic elastomer, has also been used in polypropylene-based resin compositions, but there are disadvantages in that SEBS is expensive and significantly reduces the fluidity of polypropylene.

[0006] Therefore, there is still a need to develop a thermoplastic resin composition that maintains the high fluidity of polypropylene and also has excellent impact resistance.

[0007] [Prior art literature]

[0008] [Patent Document]

[0009] (Patent Document 1) Korean Patent Application Publication No. 10-1657925. Summary of the invention

[0010] Technical issues

[0011] One aspect of the present invention provides a thermoplastic resin composition having high fluidity but capable of exhibiting excellent mechanical strength and significantly improved impact strength performance.

[0012] Technical solution

[0013] According to one aspect of the present invention, there is provided a thermoplastic resin composition comprising: (1) polypropylene; and (2) a polyolefin-polystyrene multi-block copolymer, the multi-block copolymer satisfying the following conditions (a) to (c) measured by gel permeation chromatography (GPC) and the following condition (d) measured in 13 13C NMR (500 MHz, tetrachloroethane-d2, standard substance TMS) spectrum:

[0014] (a) The weight average molecular weight is 50,000 to 300,000 g / mol,

[0015] (b) The molecular weight distribution is 1.5 to 3.0,

[0016] (c) For the measurement result of gel permeation chromatography, the Gaussian function modeled by the graph with logMw as the x-axis and dw / dlogMw as the y-axis is represented by the following mathematical formula 1, where in the following mathematical formula 1, each constant value satisfies -0.05 < A < 0.06, 4.6 < B < 5.5, 0.9 < C < 1.1, and 0.5 < D < 0.9,

[0017] (d) The polyolefin block contained in the polyolefin-polystyrene multi-block copolymer contains one or more branching points, wherein the carbon atoms of the branching points show peaks at 36 ppm to 40 ppm, and the terminal carbon atoms of the branched chains branched from the branching points show peaks at 13 ppm to 15 ppm.

[0018] [Mathematical formula 1]

[0019]

[0020] (In the above mathematical formula 1, Mw represents the weight average molecular weight of the polyolefin-polystyrene multi-block copolymer.)

[0021] Beneficial effects

[0022] The thermoplastic resin composition of the present invention has significantly improved impact strength performance and high fluidity, and thus can exhibit excellent molding processability. Description of the drawings

[0023] Figure 1 Shows the ligand compound used in the preparation of the polyolefin-polystyrene multi-block copolymer contained in the thermoplastic resin composition according to an embodiment of the present invention1 H NMR and 13 C NMR spectrum;

[0024] Figure 2 The transition metal compound used in the preparation of the polyolefin-polystyrene-based multi-block copolymer included in the thermoplastic resin composition according to an embodiment of the present invention is shown. 1 H NMR and 13 CNMR spectrum; and

[0025] Figure 3 is a diagram showing a polyolefin-polystyrene-based multi-block copolymer included in a thermoplastic resin composition according to an embodiment of the present invention by Mathematical Formula 1. DETAILED DESCRIPTION

[0026] Hereinafter, the present invention will be described in more detail to facilitate understanding of the present invention.

[0027] It should be understood that the words or terms used in the description and claims of the present invention should not be interpreted as being limited to the meanings defined in commonly used dictionaries. It will be further understood that these words or terms should be interpreted as having meanings consistent with their meanings in the relevant technical background and the technical ideas of the present invention based on the principle that the inventor can appropriately define the meanings of these words or terms to best explain the present invention.

[0028] As used herein, the term "composition" includes not only reaction products and decomposition products formed from the materials of the corresponding composition, but also includes mixtures of materials comprising the corresponding composition.

[0029] The term "polymer" as used herein refers to a polymer compound prepared by polymerizing monomers, whether of the same or different types. Thus, the generic term "polymer" encompasses the term "homopolymer" (usually employed to refer to polymers prepared from only one type of monomer) and the term "interpolymer" as defined below.

[0030] The term "interpolymer" as used herein refers to a polymer prepared by the polymerization of at least two different monomers. Thus, the general term "interpolymer" encompasses the term "copolymer" (usually used to refer to a polymer prepared from two different monomers) and the term "polymer" prepared from more than two different monomers.

[0031] Hereinafter, the present invention will be described in detail.

[0032] The thermoplastic resin composition of the present invention comprises (1) polypropylene and (2) a polyolefin-polystyrene multi-block copolymer, wherein the polyolefin-polystyrene multi-block copolymer satisfies the following conditions (a) to (c) as measured by gel permeation chromatography (GPC) and 13The following condition (d) measured in the 13C NMR (500 MHz, dichloroethane-d2, standard substance TMS) spectrum:

[0033] (a) The weight-average molecular weight is 50,000 to 300,000 g / mol,

[0034] (b) The molecular weight distribution is 1.5 to 3.0,

[0035] (c) For the measurement result of gel permeation chromatography, the Gaussian function modeled by the curve with logMw as the x-axis and dw / dlogMw as the y-axis is represented by the following mathematical formula 1, where in the following mathematical formula 1, each constant value satisfies -0.05 < A < 0.06, 4.6 < B < 5.5, 0.9 < C < 1.1, and 0.5 < D < 0.9,

[0036] (d) The polyolefin block contained in the polyolefin-polystyrene multi-block copolymer contains one or more branching points, where the carbon atoms of the branching points show peaks at 36 ppm to 40 ppm, and the terminal carbon atoms of the branched chains branched from the branching points show peaks at 13 ppm to 15 ppm.

[0037] [Mathematical formula 1]

[0038]

[0039] (In mathematical formula 1, Mw represents the weight-average molecular weight of the polyolefin-polystyrene multi-block copolymer.)

[0040] Hereinafter, each component will be described in detail.

[0041] (1) Polypropylene

[0042] In the thermoplastic resin composition according to an embodiment of the present invention, the polypropylene may specifically be a polypropylene homopolymer or a copolymer of propylene and an α-olefin monomer, where the copolymer may be an alternating, random, or block copolymer.

[0043] The α-olefin monomer may specifically be an aliphatic olefin having 2 to 12 carbon atoms, or 2 to 8 carbon atoms. More specifically, examples thereof may be ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, or 3,4-dimethyl-1-hexene, etc., and any one or a mixture of two or more thereof may be used.

[0044] More specifically, the polypropylene may be any one or a mixture of two or more selected from the group consisting of polypropylene copolymers, propylene-α-olefin copolymers and propylene-ethylene-α-olefin copolymers, wherein the copolymer may be a random or block copolymer.

[0045] In addition, the melt index (MI) of the polypropylene measured at 230° C. and a load of 2.16 kg may be 0.5 g / 10 min to 100 g / 10 min. Specifically, the melt index (MI) may be 1 g / 10 min to 90 g / 10 min. When the melt index of the polypropylene exceeds the above range, there is a possibility that problems may occur during the injection molding process of the thermoplastic resin composition.

[0046] Specifically, in the thermoplastic resin composition according to an embodiment of the present invention, the polypropylene may be an impact copolymer having a melt index (MI) of 0.5 g / 10 min to 100 g / 10 min, particularly 1 g / 10 min to 90 g / 10 min, measured at 230° C. and a load of 2.16 kg, or more specifically, a polypropylene-ethylene impact copolymer. When an impact copolymer having the above physical properties is included as the polypropylene within the above content range, impact strength properties may be improved, particularly room temperature strength properties may be improved.

[0047] The impact copolymer may be included in an amount of 10 to 90 wt %, specifically 20 to 80 wt %, and more specifically 40 to 60 wt %, based on the total weight of the thermoplastic resin composition.

[0048] The impact copolymer can be prepared by a typical polymer preparation reaction to meet the above physical property requirements, or it can be commercially obtained and used. A specific example thereof can include LG Chemical's product SEETEC TM M1600, etc.

[0049] In addition, in the thermoplastic resin composition according to an embodiment of the present invention, the polypropylene may specifically be one or more random propylene copolymers having a DSC melting point in the range of 120 to 160° C. and a melt flow rate (MFR) of 5 to 120 g / 10 min as measured under the conditions of 230° C. and 2.16 kg load according to ASTM-D 1238.

[0050] When the content of the polypropylene having the above physical properties is within the above content range, the mechanical strength (eg, hardness) of the thermoplastic resin composition may be improved.

[0051] Based on the total weight of the thermoplastic resin composition, the content of the random propylene copolymer can be 10% by weight to 90% by weight, particularly 20% by weight to 80% by weight, and more particularly 40% by weight to 60% by weight.

[0052] The random propylene copolymer can be prepared by typical polymer preparation reactions to meet the above physical property requirements, or can be commercially obtained and used. Specific examples thereof may include Braskem of Braskem America Inc. TM PP R7021-50RNA, Formolene of Formosa Plastics Corporation, USA TM 7320A, etc.

[0053] (2) Polyolefin-polystyrene multi-block copolymer

[0054] In the thermoplastic resin composition of the present invention, the polyolefin-polystyrene multi-block copolymer is characterized by satisfying the following conditions (a) to (c) measured by gel permeation chromatography (GPC) and the following condition (d) measured in the 13 13C NMR (500 MHz, tetrachloroethane-d2, standard substance TMS) spectrum:

[0055] (a) The weight average molecular weight is 50,000 to 300,000 g / mol,

[0056] (b) The molecular weight distribution is 1.5 to 3.0,

[0057] (c) For the measurement results of gel permeation chromatography, the Gaussian function modeled by the curve graph with logMw as the x-axis and dw / dlogMw as the y-axis is represented by the following mathematical formula 1, where, in the following mathematical formula 1, each constant value satisfies -0.05 < A < 0.06, 4.6 < B < 5.5, 0.9 < C < 1.1, and 0.5 < D < 0.9, and

[0058] (d) The polyolefin block contained in the polyolefin-polystyrene multi-block copolymer contains one or more branching points, where the carbon atoms of the branching points show peaks at 36 ppm to 40 ppm, and the terminal carbon atoms of the branched chains branched from the branching points show peaks at 13 ppm to 15 ppm.

[0059] [Mathematical formula 1]

[0060]

[0061] (In the above mathematical formula 1, Mw represents the weight average molecular weight of the polyolefin-polystyrene multi-block copolymer.)

[0062] The polyolefin-polystyrene multi-block copolymer contained in the thermoplastic resin composition of the present invention is prepared using a specific transition metal compound having a novel structure described below, and has a weight average molecular weight satisfying Mathematical Formula 1, which is an important factor in determining the physical properties of the copolymer. Therefore, it has a weight average molecular weight and a molecular weight distribution value with a specific distribution to achieve excellent tensile properties (e.g., tensile strength, elongation, modulus, etc.).

[0063] Regarding condition (a), the weight average molecular weight of the polyolefin-polystyrene multi-block copolymer can be 50,000 to 300,000 g / mol, particularly 60,000 to 250,000 g / mol, or 70,000 to 220,000 g / mol, or 70,000 to 200,000 g / mol.

[0064] Regarding condition (b), the molecular weight distribution of the polyolefin-polystyrene multi-block copolymer can be 1.5 to 3.0, particularly 1.6 to 2.3, or 1.6 to 2.2.

[0065] The weight average molecular weight and the number average molecular weight are polystyrene-equivalent molecular weights analyzed by gel permeation chromatography (GPC), and the molecular weight distribution is calculated by the ratio of (weight average molecular weight) / (number average molecular weight).

[0066] As described later, Mathematical Formula 1 of condition (c) represents a Gaussian distribution, and the constants B to D contained therein are used as constant values representing the weight average molecular weight and the molecular weight distribution of the copolymer. The polyolefin-polystyrene multi-block copolymer contained in the thermoplastic resin composition of the present invention satisfies the numerical ranges of A to D, and at the same time satisfies the weight average molecular weight and the molecular weight distribution values of conditions (a) and (b).

[0067] Regarding condition (c), for the gel permeation chromatography measurement results, when the following Mathematical Formula 1 is derived from the Gaussian function modeled by the graph with logMw as the x-axis and dw / dlogMw as the y-axis, each constant value contained in Mathematical Formula 1 satisfies -0.05 < A < 0.06, 4.6 < B < 5.5, 0.9 < C < 1.1, and 0.5 < D < 0.9. Specifically, the A constant can be greater than -0.05, greater than -0.04, less than 0.060, or less than 0.040, the B constant can be greater than 4.6, less than 5.5, or less than 5.2, the C constant can be greater than 0.90, greater than 0.91, less than 1.1, or less than 1.09, and the D constant can be greater than 0.5, greater than 0.6, less than 0.9, or less than 0.8.

[0068] The above mathematical formula 1 represents a differential molecular weight distribution curve, wherein the horizontal axis is "(log(Mw))", which is the logarithmic value of the weight average molecular weight (Mw) measured by gel permeation chromatography using polystyrene as the conversion standard as described above, and the vertical axis is "dw / dlog(Mw)", which is the value obtained by differentiating the concentration fraction (w) by the logarithmic value of the weight average molecular weight (log(Mw)), and can be regarded as representing the weight fraction of the polymer having the corresponding molecular weight according to the logarithmic value of the weight average molecular weight.

[0069] That is, in the present invention, a Gaussian function modeled by a graph with logMw on the x-axis and dw / dlogMw on the y-axis is represented by the following Mathematical Formula 1, and when the values ​​of constants A to D are calculated, it is newly found that each of them belongs to a specific range.

[0070] In the above mathematical formula 1, A to D constants are constants representing a curve represented by Gaussian distribution, and show the height of the distribution curve, the width of the maximum peak half value, the center position indicated by the maximum peak, etc. More specifically, the A constant contained in the Gaussian distribution represents the y intercept, and the C constant represents the arithmetic meaning of the graph area. In addition, the B and D constants represent the physical properties of the copolymer corresponding to the weight average molecular weight and the molecular weight distribution.

[0071] Regarding condition (d), the polyolefin block contained in the polyolefin-polystyrene-based multi-block copolymer includes one or more branching points, wherein the carbon atoms of the branching points show a peak of 36 to 40 ppm, and the terminal carbon atoms of the branches branched from the branching points show a peak of 13 to 15 ppm.

[0072] Specifically, the carbon atom of the branch point can show 36.0ppm or more, 37.0ppm or more, or can be 40.0ppm or less, 39.0ppm or less, or 38.5ppm or less. In addition, the terminal carbon atom of the branched chain branched from the branch point can show a peak of 13.0ppm or more, or can be 15.0ppm or less, or 14.5ppm or less.

[0073] As described above, the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention has long chain branches in the polyolefin blocks, which can be obtained by the terminal carbon atoms of the branches branched from the branching points. 13 Due to the above characteristics, the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention exhibits excellent physical properties, such as high impact strength, compared with conventional copolymers.

[0074] The polyolefin-polystyrene multi-block copolymer can be one or more selected from the group consisting of polystyrene-poly(ethylene-co-propylene)-polystyrene block copolymer, polystyrene-poly(ethylene-co-1-butene)-polystyrene block copolymer, polystyrene-poly(ethylene-co-1-pentene)-polystyrene block copolymer, polystyrene-poly(ethylene-co-1-hexene)-polystyrene block copolymer, polystyrene-poly(ethylene-co-1-heptene)-polystyrene block copolymer and polystyrene-poly(ethylene-co-1-octene)-polystyrene block copolymer.

[0075] Furthermore, the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention satisfies the conditions (a) to (d) and can therefore have the following tensile properties.

[0076] Specifically, the polyolefin-polystyrene-based multi-block copolymer may have a tensile strength of 10 to 100 MPa, specifically 10 to 50 MPa, and more specifically 20 to 40 MPa, wherein the tensile strength refers to the maximum tensile stress when stretched and broken in order to uniformly apply a load to a cross-sectional area.

[0077] The polyolefin-polystyrene-based multi-block copolymer may have an elongation at break of 500% to 3,000%, 600% to 2,800%, or 800% to 2,500%, wherein the elongation at break is expressed as a percentage of an increased length as a deformation in a stretching direction due to stretching to an original length.

[0078] The 300% modulus of the polyolefin-polystyrene multi-block copolymer is 2.1 to 10.0 MPa, wherein the 300% modulus is expressed as an average force per unit area as tensile stress when 300% elongation is given.

[0079] Tensile properties such as tensile strength, elongation at break, 300% modulus, etc. can be measured by the standard measurement method of ASTM D412.

[0080] As described above, the polyolefin-polystyrene multi-block copolymer contained in the thermoplastic resin composition of the present invention satisfies the tensile strength, elongation at break and 300% modulus within the above ranges, and exhibits excellent physical properties compared to conventional copolymers. In addition, by adjusting the length and content of the polyolefin block using the manufacturing method provided by the present invention, a copolymer having specific properties according to the desired use can be prepared.

[0081] Furthermore, the polyolefin-polystyrene-based multi-block copolymer included in the thermoplastic resin composition of the present invention may include one or more repeating units represented by the following Chemical Formula a.

[0082] [Chemical Formula a]

[0083]

[0084] In the above Chemical Formula a,

[0085] R1 can be hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with a silyl group, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms substituted with a silyl group, and

[0086] n can be an integer from 1 to 10,000.

[0087] Alternatively, according to an embodiment of the present invention, R1 can be hydrogen or an alkyl group having 3 to 20 carbon atoms.

[0088] Alternatively, according to an embodiment of the present invention, R1 can be hydrogen or an alkyl group having 3 to 12 carbon atoms. In particular, R1 can be hydrogen or an alkyl group having 4 to 12 carbon atoms.

[0089] Alternatively, n can be an integer from 10 to 10,000. In particular, n can be an integer from 500 to 7,000.

[0090] Meanwhile, in the chemical formulas shown in the specification of the present invention, "*" is the terminal part of the repeating unit and represents the connection site.

[0091] When the polyolefin block includes two or more repeating units represented by the above Chemical Formula a, the polyolefin block can include the repeating unit represented by the following Chemical Formula b.

[0092] [Chemical Formula b]

[0093]

[0094] In the above Chemical Formula b.

[0095] R1' and R1" are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with a silyl group, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms substituted with a silyl group, where R1' and R1" are different from each other.

[0096] 0 < p < 1, and

[0097] n' can be an integer from 1 to 10,000.

[0098] Alternatively, according to one embodiment of the present invention, R1' and R1" may each independently be hydrogen or an alkyl group having 3 to 20 carbon atoms, particularly may each independently be hydrogen or an alkyl group having 3 to 12 carbon atoms, more particularly may each independently be hydrogen or an alkyl group having 4 to 12 carbon atoms.

[0099] Alternatively, n' may specifically be an integer of 10 to 10,000, and more specifically may be an integer of 500 to 7,000.

[0100] According to one embodiment of the present invention, in the above chemical formula b, any one of R1′ and R1″ may be hydrogen, and the other thereof may be a substituent other than hydrogen among the above substituents.

[0101] That is, when the polyolefin block includes two or more repeating units represented by the above chemical formula a, a structure in which R1 is hydrogen and a structure in which R1 is an alkyl group having 1 to 20 carbon atoms other than hydrogen, an alkyl group having 1 to 20 carbon atoms substituted with a silyl group, an arylalkyl group having 7 to 20 carbon atoms, or a structure in which R1 is an alkyl group having 7 to 20 carbon atoms substituted with a silyl group may be randomly connected. In particular, a structure in which R1 is hydrogen and a structure in which R1 is an alkyl group having 3 to 20 carbon atoms other than hydrogen may be randomly connected.

[0102] Alternatively, more specifically, the polyolefin block may have a structure in which R1 is hydrogen and a structure in which R1 is an alkyl group having 3 to 12 carbon atoms randomly connected to each other. Still more specifically, the polyolefin block may have a structure in which R1 is hydrogen and a structure in which R1 is an alkyl group having 4 to 12 carbon atoms randomly connected to each other.

[0103] When the polyolefin block includes two or more repeating units represented by the above Chemical Formula a, the polyolefin block may include a structure in which R1 is hydrogen and a structure in which R1 has a substituent other than hydrogen in the above Chemical Formula a at a weight ratio of 30:90 to 70:10, specifically at a weight ratio of 40:60 to 60:40, more specifically at a weight ratio of 45:75 to 55:25.

[0104] When the polyolefin block includes a structure in which R1 in the above chemical formula a is hydrogen and a structure in which R1 has a substituent other than hydrogen within the above range, the prepared block copolymer includes an appropriate degree of branching in the structure, and therefore has a very high 300% modulus value and a very high elongation at break value, thereby showing excellent elastic properties, and also shows a high molecular weight and a wide molecular weight distribution, and therefore, can have excellent processability.

[0105] Furthermore, the first polystyrene block of the polyolefin-polystyrene-based multi-block copolymer included in the thermoplastic resin composition of the present invention may include one or more repeating units represented by the following Chemical Formula c.

[0106] [Chemical formula c]

[0107]

[0108] In the above chemical formula c,

[0109] R2 is an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and

[0110] l is an integer from 10 to 1,000.

[0111] R2 may be phenyl, or phenyl which is unsubstituted or substituted with halogen, alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 12 carbon atoms, alkoxy of 1 to 8 carbon atoms, or aryl of 6 to 12 carbon atoms. Alternatively, R2 may be phenyl.

[0112] l is an integer of 10 to 1,000, and specifically may be an integer of 50 to 700. When l is within the above range, the viscosity of the polyolefin-polystyrene block copolymer produced by the production method of the present invention may be at an appropriate level.

[0113] In particular, in the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention, the polyolefin block including the repeating unit represented by the above Chemical Formula a and the first polystyrene block including the repeating unit represented by the above Chemical Formula c can be combined with each other to form a composite block represented by the following Chemical Formula d.

[0114] [Chemical formula d]

[0115]

[0116] In the above chemical formula d,

[0117] R1 may be hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with a silyl group, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms substituted with a silyl group, and

[0118] R2 is an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms,

[0119] l is an integer from 10 to 1,000, and

[0120] n is an integer from 1 to 10,000.

[0121] Alternatively, in the above Chemical Formula d, R1, R2, l and n are the same as defined in Chemical Formula a and Chemical Formula c, respectively.

[0122] Alternatively, when the polyolefin block includes the repeating unit represented by the above Chemical Formula a, the composite block formed by combining the first polystyrene block including the repeating unit represented by the above Chemical Formula c may be represented by the following Chemical Formula e.

[0123] [Chemical formula e]

[0124]

[0125] In the above chemical formula e, R1′, R1″, R2, p, l and n′ are the same as defined in chemical formula a or c, respectively.

[0126] In addition, in one example of the present invention, when preparing a polyolefin-polystyrene multi-block copolymer, a styrene monomer may form a polyolefin block, and a styrene monomer may simultaneously combine with an organic zinc compound and polymerize to form another styrene polymer block. In the present disclosure, the other styrene polymer block is represented as a second polystyrene block. The second polystyrene block may include a repeating unit represented by the following chemical formula f.

[0127] [Chemical formula f]

[0128]

[0129] In the above chemical formula f,

[0130] R3 is an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and

[0131] m is an integer from 10 to 1,000.

[0132] Alternatively, according to one embodiment of the present invention, R3 may be a phenyl group, or a phenyl group which is unsubstituted or substituted with a halogen, an alkyl group of 1 to 8 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an aryl group of 6 to 12 carbon atoms. Alternatively, R3 may be a phenyl group.

[0133] m is an integer of 10 to 1,000, and specifically may be an integer of 50 to 700.

[0134] That is, the polyolefin-polystyrene-based multi-block copolymer included in the thermoplastic resin composition of the present invention may include a first polystyrene block including a repeating unit represented by the above Chemical Formula c, and a second polystyrene block represented by the above Chemical Formula f.

[0135] Therefore, the block copolymer composition may include a triblock copolymer comprising a polyolefin block comprising one or more repeating units represented by the following Chemical Formula a, a first polystyrene block comprising a repeating unit represented by the following Chemical Formula c, and a second polystyrene block comprising a repeating unit represented by the following Chemical Formula f.

[0136] [Chemical formula a]

[0137]

[0138] [Chemical formula c]

[0139]

[0140] [Chemical formula f]

[0141]

[0142] In the above chemical formula,

[0143] R1 is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with a silyl group, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms substituted with a silyl group,

[0144] R2 and R3 are each independently an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms,

[0145] n is an integer from 10 to 10,000, and

[0146] l and m are each independently an integer of 10 to 1,000.

[0147] Alternatively, in the above chemical formula, R1, R2, R3, n, l and m are the same as defined in chemical formulas a, c and f, respectively.

[0148] Preparation method of polyolefin-polystyrene multi-block copolymer

[0149] A method for preparing a polyolefin-polystyrene multi-block copolymer, characterized by comprising: (S1) in the presence of a catalyst composition comprising a transition metal compound represented by the following chemical formula 1, by polymerizing olefin monomers to form polyolefin blocks by using an organic zinc compound as a chain transfer agent, and (S2) in the presence of an alkyl lithium compound containing a silicon atom and a triamine compound, by anionic polymerization of the polyolefin blocks and styrene monomers to form polystyrene blocks.

[0150] The method for preparing a polyolefin-polystyrene multi-block copolymer can form a polyolefin chain by using a transition metal compound represented by Chemical Formula 1 which is effective for polymerization of an olefin monomer as a catalyst, and then continuously performing styrene anion polymerization to form a polyolefin-polystyrene block described later, thereby forming a polyolefin-polystyrene multi-block copolymer showing a specific height of a tan δ peak and a tan δ peak half width.

[0151] Step (S1)

[0152] The step (S1) is a step of forming a polyolefin block by polymerizing an olefin-based monomer using an organic zinc compound as a chain transfer agent in the presence of a catalyst composition including a transition metal compound represented by the following Chemical Formula 1.

[0153] [Chemical formula 1]

[0154]

[0155] In the above chemical formula 1,

[0156] R1 to R 11 each independently represents hydrogen, an 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 arylalkoxy group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

[0157] R1 to R 11 Two or more adjacent ones of the rings may be connected to each other to form an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, and

[0158] X1 and X2 are each independently hydrogen, halogen, hydroxyl, amino, thiol, silyl, cyano, nitro, an 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, an aryloxy group having 6 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an arylsilyl group having 6 to 20 carbon atoms.

[0159] When the polymerization reaction is carried out in the presence of an excess of chain transfer agent (e.g., (Et)2Zn) relative to the catalyst, the olefin polymer chain causes a rapid alkyl transfer between zinc (Zn) and hafnium (Hf), thereby uniformly growing from dialkyl zinc, thereby achieving active polymerization, which is called coordination chain transfer polymerization (CCTP). Commonly used metallocene catalysts cannot be active polymerized by a β-elimination process, and the few catalysts known to be suitable for CCTP only allow a single polymerization of ethylene and α-olefins, making it very difficult to polymerize ethylene and α-olefins by CCTP. Therefore, it is very difficult to use common transition metal compounds as catalysts to perform active polymerization and prepare block copolymers by CCTP.

[0160] On the other hand, the hafnium compound represented by the above Chemical Formula 1 is [N 酰胺基 ,N,C 芳基 ]HfMe2 type complexes exhibit excellent α-olefin introduction ability in the polymerization of ethylene and α-olefin. In particular, the molecular weight of the olefin polymer or the content of α-olefin varies with the content of the chain transfer agent, which shows that the compound can be successfully used in CCTP, and the β-elimination reaction rarely occurs, which is enough to be ignored. That is, the polymerization of ethylene and α-olefin monomers can be carried out by CCTP using the hafnium compound represented by the above chemical formula 1 as living polymerization, and block copolymers with various block compositions can be successfully prepared.

[0161] In addition, CCTP can be converted using hafnium compounds and subjected to anionic styrene polymerization to synthesize polyolefin-polystyrene block copolymers. As described above, hafnium compounds can be used as catalysts for preparing olefin polymers, which is a unique feature that can be achieved by the novel structure of the hafnium compound represented by Chemical Formula 1 above.

[0162] Specifically, in the above chemical formula 1, R1 to R 11 R1 to R2 may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. 10 can be hydrogen, and R 11 It may be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. 10 can be hydrogen, and R 11 It may be hydrogen or an alkyl group having 1 to 20 carbon atoms.

[0163] Alternatively, in the above Chemical Formula 1, R1 to R 11 R3 and R4 may be independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. In this case, R3 and R4 may be connected to each other to form an aromatic ring having 5 to 20 carbon atoms, such as a benzene ring. Preferably, R3 and R4 may be connected to each other to form a benzene ring, and at the same time, R 11 It may be an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0164] Alternatively, in the above Chemical Formula 1, R1, R2 and R5 to R 10 can be hydrogen, R3, R4 and R 11 Each may independently be hydrogen or an alkyl group having 1 to 20 carbon atoms, wherein R3 and R4 may be linked to each other to form an aromatic ring having 5 to 20 carbon atoms, such as a benzene ring.

[0165] Meanwhile, X1 and X2 may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and preferably, may each independently be an alkyl group having 1 to 20 carbon atoms, wherein X1 and X2 may be the same as each other.

[0166] In the present invention, the term "alkyl" refers to a straight-chain or branched hydrocarbon moiety.

[0167] In the present invention, the term "alkenyl group" refers to a linear or branched alkenyl group.

[0168] In the present invention, the "aryl group" preferably has 6 to 20 carbon atoms, and specifically may be phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilino, anisole, etc., but is not limited thereto.

[0169] In the present invention, "alkylaryl" refers to an aryl group substituted with the above alkyl group.

[0170] In the present invention, the "arylalkyl group" refers to an alkyl group substituted with the above aryl group.

[0171] In the present specification, the "alkylsilyl group" may be a silyl group substituted with an alkyl group having 1 to 20 carbon atoms, for example, a trimethylsilyl group or a triethylsilyl group.

[0172] In the present invention, "alkylamino" refers to an amino group substituted by the above alkyl groups, such as dimethylamino, diethylamino, etc., but is not limited thereto.

[0173] In the present invention, unless otherwise specified, "hydrocarbon group" means a monovalent hydrocarbon group having 1 to 20 carbon atoms and consisting only of carbon and hydrogen, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkaryl or aralkyl, regardless of its structure.

[0174] More specifically, the hafnium compound represented by the above Chemical Formula 1 may be a hafnium compound represented by the following Chemical Formula 1a or 1b.

[0175] [Chemical formula 1a]

[0176]

[0177] [Chemical formula 1b]

[0178]

[0179] In the above Chemical Formula 1a and Chemical Formula 1b,

[0180] R 11 is hydrogen, an 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 arylalkoxy group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and

[0181] X1 and X2 are each independently hydrogen, halogen, hydroxyl, amino, thiol, silyl, cyano, nitro, an 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, an aryloxy group having 6 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an arylsilyl group having 6 to 20 carbon atoms.

[0182] The hafnium compound may be represented by any one of Chemical Formula 1-1 to Chemical Formula 1-5, but is not limited thereto. Any hafnium compound corresponding to Chemical Formula 1 is included in the present invention.

[0183] [Chemical formula 1-1]

[0184]

[0185] [Chemical formula 1-2]

[0186]

[0187] [Chemical formula 1-3]

[0188]

[0189] [Chemical formula 1-4]

[0190]

[0191] [Chemical formula 1-5]

[0192]

[0193] The hafnium compound of the present invention may be prepared by a step including reacting a compound represented by the following Chemical Formula 2 with a compound represented by the following Chemical Formula 3.

[0194] [Chemical formula 2]

[0195]

[0196] [Chemical formula 3]

[0197] Hf(X1X2)2

[0198] In the above chemical formula,

[0199] R1 to R 11 and X1 and X2 are defined the same as above.

[0200] Meanwhile, when the hafnium compound represented by the above Chemical Formula 1 is prepared, the step of preparing the ligand compound may be variously performed as follows depending on the structure of the finally prepared hafnium compound.

[0201] For example, when R3 and R4 in the ligand compound do not form a ring with each other and R 11 When it is a hydrogen atom, as shown below, the ligand compound can be hydrogenated under a ruthenium catalyst and then reacted with a compound represented by Chemical Formula 3 as a hafnium precursor to prepare a hafnium compound.

[0202] [Reaction formula 1]

[0203]

[0204] Alternatively, when R3 and R4 do not form a ring with each other in the ligand compound structure and R 11 When it is a substituent other than a hydrogen atom, as shown in the following reaction formula 2, an organic lithium compound is first used to introduce R 11 , and then hydrogenated under a ruthenium catalyst to prepare a ligand compound.

[0205] [Reaction 2]

[0206]

[0207] Alternatively, when R3 and R4 are linked to each other to form an aromatic ring having 5 to 20 carbon atoms in the ligand compound structure and R 11 When R is a substituent other than a hydrogen atom, an organolithium compound can be used to introduce R as shown below. 11 , and then, in order to prevent the hydrogenation of aromatic rings such as naphthyl, hydrogenation was carried out over a Pd / C catalyst to prepare a ligand compound.

[0208] [Reaction 3]

[0209]

[0210] That is, the hafnium compound can be prepared by preparing the ligand compound by alkylating and hydrogenating a compound as a precursor of the ligand compound under suitable reagents and reaction conditions, and then introducing hafnium therein to prepare the hafnium compound. Considering the structure of the final compound and experimental conditions, those skilled in the art can appropriately change the specific type of the alkylating agent, the reaction temperature and pressure, etc.

[0211] In the present invention, the organic zinc compound is a material used as a chain transfer agent, which induces chain transfer in a preparation process of a polymerization reaction to prepare a copolymer, and may be specifically a compound represented by the following Chemical Formula 4.

[0212] [Chemical formula 4]

[0213]

[0214] In the above chemical formula 4,

[0215] A is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms substituted with halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and

[0216] B is an arylene group having 6 to 12 carbon atoms substituted with an alkenyl group having 2 to 12 carbon atoms.

[0217] Alternatively, A may be an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms substituted with halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and

[0218] B may be an arylene group having 6 to 12 carbon atoms substituted with an alkenyl group having 2 to 18 carbon atoms.

[0219] Chemical Formula 4 may have a structure in which both ends of the chemical formula are double bonds. For example, when B is an arylene group substituted with an alkenyl group, the arylene group is connected to A and the double bond of the alkenyl group substituted in the arylene group may be located at the outermost portion of Chemical Formula 4.

[0220] When the organozinc compound reacts with one or more olefinic monomers in the presence of the catalyst composition, the olefinic monomers may be inserted between zinc (Zn) of the organozinc compound and the organic group (A) to achieve polymerization.

[0221] The mixed amount of the organic zinc compound may be 1 to 200 equivalents based on 1 equivalent of the transition metal compound of Chemical Formula 1, and specifically, 10 to 100 equivalents based on 1 equivalent of the transition metal compound of Chemical Formula 1.

[0222] The organozinc compound does not contain impurities such as THF and a large amount of magnesium salts and thus can be provided in high purity, and thus can be used as a chain transfer agent and facilitates olefin polymerization.

[0223] The catalyst composition may further include a co-catalyst compound. At this time, the co-catalyst compound is used to activate the transition metal compound represented by Chemical Formula 1, and as a co-catalyst, those known in the art can be used. For example, one or more selected from the following Chemical Formulas 5 to 7 can be used as a co-catalyst.

[0224] [Chemical formula 5]

[0225] -[Al(R a )-O] m -

[0226] [Chemical formula 6]

[0227] D(R a )3

[0228] [Chemical formula 7]

[0229] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0230] In the above chemical formula,

[0231] R a are each independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen,

[0232] m is an integer greater than or equal to 2,

[0233] D is aluminum or boron,

[0234] L is a neutral or cationic Lewis acid,

[0235] Z is a Group 13 element,

[0236] A is each independently an aryl group having 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, or an alkyl group having 1 to 20 carbon atoms, and

[0237] The substituent of A is a halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0238] The compound represented by the above Chemical Formula 5 is not particularly limited as long as it is an alkylaluminoxane. Preferred examples thereof include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and a particularly preferred compound is methylaluminoxane.

[0239] The compound represented by the above Chemical Formula 6 is not particularly limited, but preferred examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc. Particularly preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

[0240] Examples of the compound represented by the above Chemical Formula 7 include: when Z is boron, for example, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] -, dioctadecylmethylammonium tetra(phenyl)borate, dioctadecylmethylammonium tetra[3,5-bis(trifluoromethyl)phenyl]borate, tetra(phenyl)borate, triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(pentafluorophenyl)borate, N, N-Diethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, diethylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetrakis(p-tolyl)borate, tripropylammonium tetrakis(p-tolyl)borate, triethylammonium tetrakis(o-p-dimethylphenyl)borate, trimethylammonium tetrakis(p-trifluoromethylphenyl)borate )tributylammonium borate, trimethylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, diethylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetraphenylborate, triphenylcarbonium tetrakis(p-trifluoromethylphenyl)borate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, or a combination thereof; when Z is aluminum, for example, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum , trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetra(pentafluorophenyl)aluminum, N,N-diethylaniline tetraphenylaluminum, N,N-diethylaniline tetra(pentafluorophenyl)aluminum, diethylammonium tetra(pentafluorophenyl)aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, or a combination thereof, but not limited thereto.

[0241] In particular, the co-catalyst used in the present invention may be a compound represented by the above Chemical Formula 7, and specifically may be dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate.

[0242] In addition, the cocatalyst used in the present invention can be prepared in an anhydrous hydrocarbon solvent. For example, the hydrocarbon solvent can be one or more selected from butane, pentane, neopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, xylene and ethylbenzene, but is not limited thereto. Any hydrocarbon solvent available in the art can be used in an anhydrous form.

[0243] In the present invention, when the co-catalyst is prepared in an anhydrous hydrocarbon solvent,1 In the H NMR spectrum, at least one peak appears in the range of 1.75 ppm to 1.90 ppm and in the range of 1.90 ppm to 2.00 ppm. This indicates that the protons connected to the α-carbon adjacent to the nitrogen, sulfur or phosphorus contained in L show different peaks. For example, when the compound represented by Chemical Formula 1 is [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] - When, in its 1 In the HNMR spectrum, the two protons present in NCH2 can each show a different signal.

[0244] In addition, the hafnium compound represented by Chemical Formula 1 and the co-catalyst may also be used in the form of being supported on a carrier. The carrier may be silica or alumina, but is not limited thereto.

[0245] The olefin monomer introduced as a reaction material in step (S1) may be ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene, or a monomer formed by a mixture thereof, etc. The olefin monomer may be used alone or in combination of two or more.

[0246] Step (S1) can be carried out, for example, in a uniform solution state. At this time, as a solvent, a hydrocarbon solvent or an olefin monomer itself can be used as a medium. The hydrocarbon solvent can be an aliphatic hydrocarbon solvent having 4 to 20 carbon atoms, specifically isobutane, hexane, cyclohexane, methylcyclohexane, etc. The solvent can be used alone or in combination of two or more.

[0247] The polymerization temperature of step (S1) may vary according to the reactants, reaction conditions, etc., but may be specifically 70 to 170° C., specifically 80 to 150° C., or 90 to 120° C. Within the above range, the solubility of the polymer may be increased and the catalyst may be thermally stabilized.

[0248] The polymerization in step (S1) may be carried out in a batch, semi-continuous or continuous manner, or in two or more steps with different reaction conditions.

[0249] The compound prepared in the above step (S1) can be used as a precursor for preparing the polyolefin-polystyrene multi-block copolymer of the present invention by anionic polymerization in the step (S2) described later.

[0250] Step (S2)

[0251] Step (S2) is a step performed subsequent to step (S1) and is a step of forming a polystyrene block by anionic polymerization of a polyolefin block and a styrene monomer in the presence of an alkyllithium compound containing a silicon atom and a triamine compound to prepare a polyolefin-polystyrene multiblock copolymer.

[0252] In step (S2), the styrene monomers can be continuously inserted between the zinc-carbon bonds of the (polyolefin group) 2Zn contained in the compound formed by the above step (S1), and at the same time, the styrene groups present at the ends of the compound formed by step (S1) can participate as copolymerization sites with the styrene monomers and be connected to the polystyrene chain. In addition, the multi-block copolymer prepared by the above method can be easily quenched by the reaction of the end groups with water, oxygen or organic acid, thereby converting the multi-block copolymer into an industrially useful polyolefin-polystyrene multi-block copolymer.

[0253] The styrene-based monomer may be a styrene-based monomer having 6 to 20 carbon atoms. More specifically, the styrene-based monomer may be a styrene-based monomer including ethylene substituted with an aromatic group having 6 to 20 carbon atoms, ethylene substituted with a phenyl group, etc., such as styrene.

[0254] The alkyl lithium compound including a silicon atom may be a compound represented by Chemical Formula 8 below.

[0255] [Chemical formula 8]

[0256] (CH3)3Si(CH2)Li

[0257] Alkyl lithium compounds containing silicon atoms are substances widely used as anionic polymerization initiators, and are easily available for use in the present invention.

[0258] The triamine compound may be a compound represented by Chemical Formula 9 below.

[0259] [Chemical formula 9]

[0260]

[0261] The triamine compound is a compound for improving the reactivity as a base or as a nucleophilic agent of an alkyl lithium compound by well coordinating with lithium, and is easily available and inexpensive.

[0262] The present invention novel uses compounds of chemical formulas 8 and 9 (e.g., Me3SiCH2Li·(PMDETA)) as initiators in step (S2), thereby suppressing the production of polystyrene homopolymers, polyolefin homopolymers, and polyolefin-polystyrene diblock copolymers, and maximizing the production of polyolefin-polystyrene multiblock copolymers, which is the purpose of the present invention.

[0263] The alkyllithium compound containing silicon atoms and represented by Chemical Formula 8 and the triamine compound represented by Chemical Formula 9 may be mixed and introduced into the aliphatic hydrocarbon solvent, or may be introduced sequentially.

[0264] The anionic polymerization temperature of step (S2) may vary depending on the reactants, reaction conditions, etc., but may be specifically 40 to 170°C, more specifically 60 to 150°C, or 90 to 100°C.

[0265] The anionic polymerization in step (S2) can be carried out in batches, semi-continuously or continuously, or in two or more steps with different reaction conditions.

[0266] The anionic polymerization time of step (S2) can vary according to the reaction materials, reaction conditions, etc., but can specifically be 0.5 to 10 hours, 1 to 8 hours, 2 to 7 hours or 4 to 6 hours. When within the above range, it is advantageous to convert the total amount of the introduced styrene monomers into a multi-block copolymer.

[0267] As described above, in the preparation method of the present invention, the polyolefin chain is grown by olefin polymerization using the above-mentioned organic zinc compound represented by the above-mentioned Chemical Formula 4, and then styrene anion polymerization is continuously performed to prepare a polyolefin-polystyrene-based multi-block copolymer, thereby effectively preparing a polyolefin-polystyrene-based multi-block copolymer having improved physical properties compared with the prior art, and thus can be easily used in industry.

[0268] The method for preparing the polyolefin-polystyrene multi-block copolymer according to the example of the present invention is different from the common method for preparing the polyolefin-polystyrene multi-block copolymer (in which styrene and diene are anion polymerized and then subjected to a two-step hydrogenation process), and is characterized in that the polyolefin-polystyrene multi-block copolymer is prepared without a hydrogenation reaction on the double bonds in the main chain of the copolymer. Therefore, the polyolefin-polystyrene multi-block copolymer contained in the thermoplastic resin composition of the present invention is characterized in that the polyolefin-polystyrene multi-block copolymer does not contain unsaturated bonds that are not saturated and exist during the hydrogenation process of the double bonds in the main chain.

[0269] At the same time, in order to meet the use and the corresponding required physical properties, the thermoplastic resin composition according to the embodiment of the present invention having the above composition may include appropriate contents of each component. For example, in the present invention, the thermoplastic resin composition may include a weight ratio of 10:90 to 90:10, particularly a weight ratio of 20:80 to 80:20, more particularly a weight ratio of 40:60 to 60:40 (1) polypropylene and (2) polyolefin-polystyrene multi-block copolymer. The thermoplastic resin composition of the present invention includes polypropylene and polyolefin-polystyrene multi-block copolymers in the above weight ratio, so improved low temperature and room temperature impact strength performance and high fluidity can be exhibited. When the content of the polyolefin-polystyrene multi-block copolymer contained in the thermoplastic resin composition is too little, the impact strength may be reduced, and when the content of the polyolefin-polystyrene multi-block copolymer is too much, the fluidity of the thermoplastic resin may be reduced. The mixing ratio can be controlled by considering the importance of the physical properties of polypropylene and polyolefin-polystyrene multi-block copolymers.

[0270] The thermoplastic resin composition of the present invention includes the polyolefin-polystyrene-based multi-block copolymer satisfying conditions (a) to (d), and thus can exhibit excellent low-temperature and room-temperature impact strength even when including the polyolefin-polystyrene-based multi-block copolymer in a relatively small amount.

[0271] The thermoplastic resin composition according to an embodiment of the present invention may optionally further include an inorganic filler along with the polypropylene and the polyolefin-polystyrene-based multi-block copolymer to improve mechanical properties of the thermoplastic resin composition.

[0272] Inorganic filler can be powder filler, sheet filler, fibrous filler or spherical filler, and can use any one thereof or a mixture of two or more thereof. Specifically, powder filler can be natural silicic acid or silicate such as fine powder talc, kaolinite, calcined clay or sericite, carbonates such as precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, hydroxides such as aluminum hydroxide or magnesium hydroxide, oxides such as zinc oxide, magnesium oxide or titanium oxide, synthetic silicic acid or silicate such as hydrated calcium silicate, hydrated aluminum silicate, hydrated silicic acid or silicic anhydride and silicon carbide, etc. In addition, sheet filler can be mica, etc. Fibrous filler can be basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, processed mineral fiber (PMF), potassium titanate, etc. In addition, spherical filler can be glass balls, etc. Wherein, inorganic filler can be talc.

[0273] Furthermore, the inorganic filler may be surface treated to improve the strength properties and molding processability of the thermoplastic resin composition.

[0274] 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.

[0275] In addition, the average particle size (D 50 ) may be 1 μm to 20 μm, specifically 3 μm to 15 μm, and more specifically 5 μm to 10 μm. When the average particle size of the inorganic filler is too small, when mixed with polypropylene and polyolefin-polystyrene multi-block copolymer, it is difficult to achieve uniform dispersion due to the aggregation between the inorganic filler particles, and as a result, the effect of improving the mechanical properties of the thermoplastic resin composition may not be significant. In addition, when the average particle size of the inorganic filler is too large, there is a risk of reduced physical properties due to reduced dispersibility of the inorganic filler itself.

[0276] In the present invention, the average particle size (D 50 ) can be defined as the particle size at 50% of the particle size distribution. In the present invention, the average particle size (D 50 ) can be measured by electron microscopy using, for example, a scanning electron microscope (SEM) or a field emission scanning electron microscope (FE-SEM) or by a laser diffraction method. Specifically, when measuring by the laser diffraction method, the inorganic filler particles can be dispersed in a dispersion medium and then introduced into a commercially available laser diffraction particle size measuring device (e.g., Microtrac MT 3000) to measure the average particle size (D ) at 50% of the particle size distribution in the measuring device. 50 ).

[0277] Based on 100 parts by weight of the thermoplastic resin composition, the content of the above-mentioned inorganic filler can be 0.1 parts by weight to 40 parts by weight. When the content of the inorganic filler in the thermoplastic resin composition is less than 0.1 parts by weight based on 100 parts by weight of the thermoplastic resin composition, the improvement effect due to the inclusion of the inorganic filler is not significant, and when it is greater than 40 parts by weight, the processability of the thermoplastic resin composition may be reduced. More specifically, based on the total weight of the thermoplastic resin composition, the content of the inorganic filler can be 0.1% by weight to 20% by weight.

[0278] The thermoplastic resin composition according to an embodiment of the present invention that meets the above composition and content conditions can be prepared by adding polypropylene and optional inorganic fillers to a polyolefin-polystyrene multi-block copolymer and then heat treating the polypropylene. At this time, the type and content of the polypropylene are the same as above.

[0279] The mixing process can be carried out according to a typical method. Specifically, a super mixer or a ribbon mixer can be used for mixing.

[0280] In addition, according to the needs of the mixing process, additives such as antioxidants, heat stabilizers, UV stabilizers, antistatic agents, etc. may also be included. In order to improve the coating properties, additives with a small amount of adhesive resin or polar groups may be selectively used within an appropriate content range.

[0281] The heat treatment process may be performed at a temperature higher than the melting point of polypropylene and not higher than 210° C. The heat treatment process may be performed using various mixing processing devices such as a twin-screw extruder, a single-screw extruder, a roll mill, a kneader, a Banbury mixer, and the like.

[0282] The thermoplastic composition according to an embodiment of the present invention prepared according to the above preparation method may exhibit excellent low-temperature impact strength properties and high fluidity, and may also exhibit excellent room-temperature impact strength properties.

[0283] In particular, the thermoplastic resin composition may satisfy the following physical properties (A) to (C).

[0284] (A) Room temperature impact strength: 3 to 100 kgf·m / m

[0285] (B) Low temperature (-40°C) impact strength: 2 to 120 kgf·m / m

[0286] (C) melt flow rate (MFR, 230°C and 2.16 kg) of 0.5 to 200 g / 10 min

[0287] (A) The room temperature impact strength measured by ASTM D256 method may be 3 to 100 kgf.m / m, specifically 20 to 100 kgf.m / m, and more specifically 30 to 90 kgf.m / m.

[0288] (B) Low temperature impact strength measured at low temperature (-40° C.) by ASTM D256 method may be 2 to 120 kgf.m / m, specifically 10 to 110 kgf.m / m, more specifically 22 to 80 kgf.m / m (-40° C.).

[0289] (C) The melt flow rate (MFR) measured at 230° C. and 2.16 kg load according to the ASTM-D 1238 method may be 0.5 to 200 g / 10 min, specifically 3 to 100 g / 10 min, more specifically 7 to 50 g / 10 min.

[0290] The thermoplastic resin composition according to an embodiment of the present invention can be used for hollow molding, extrusion molding or injection molding in various fields and applications such as packaging, construction, household goods, etc., such as automobiles, wires, toys, textiles or medical products. In particular, the thermoplastic resin composition has excellent toughness and impact strength at both low temperatures and room temperatures, and also has excellent physical properties such as heat resistance and rigidity, and can therefore be used for interior and exterior trims of automobiles.

[0291] According to another embodiment of the present invention, there are provided a molded body and an automobile part manufactured by using the thermoplastic resin composition satisfying the above physical property requirements.

[0292] The molded body may specifically be a blow molded body, an inflation molded body, a cast molded body, an extrusion laminated body, an extrusion molded body, a foamed body, an injection molded body, a sheet, a film, a fiber, a monofilament, a nonwoven fabric, or the like.

[0293] In addition, the automobile parts may be interior and exterior trims of an automobile, etc.

[0294] Example

[0295] Hereinafter, the present invention will be described in detail with reference to Examples. However, the following Examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.

[0296] <Preparation of transition metal compound>

[0297] Preparation Example 1

[0298] (i) Preparation of ligand compounds

[0299] Isopropyl lithium (0.45 mL, 0.36 mmol, 0.79 M pentane solution) was slowly added to 2-naphthyl-1,10-phenanthroline (0.789 g, 2.58 mmol) in toluene (8 mL) at -10 ° C. After stirring at room temperature for 3 hours, degassed H2O (3 mL) was added. The water layer was removed by a syringe under N2. The solvent was removed using a vacuum line, and the residue was dissolved in degassed ethanol (15 mL) and THF (5 mL). The solution was transferred to a bomb reactor containing Pd / C (0.242 mmol, 10 mol%) under N2. After H2 gas was charged to 5 bar, the mixture was stirred at room temperature for 12 hours. H2 gas was released and the catalyst residue was filtered on diatomaceous earth and removed. The solvent was removed and the residue was purified by silica gel column chromatography using ethyl acetate / hexane (1 / 3, v / v). A light yellow viscous solid (0.085 g, 73%) was obtained. 1 H NMR and 13 C NMR spectrum is shown in Figure 1 middle.

[0300] - 1 H NMR (C6D6): δ8.58(d,J=7.8Hz,H),7.75(d,J=9.0Hz,H),7.70(d,J=9.6Hz,H),7.66(d, J=7.2Hz,H),7.63(d,J=6.6Hz,H),7.32(m,4H),7.18(d,J=8.4Hz,H),6.99(d,J=7.8Hz ,H),6.39(s,H,NH),2.93(m,H),2.79(m,H),2.70(dt,J=4.8Hz,H),1.70(m,H),1.63(m ,H),1.47(m,H),0.81(d,J=7.2Hz,3H,CH(CH3)2),0.76(d,J=7.2Hz,3H,CH(CH3)2)ppm.

[0301] - 13 C{ 1 H}NMR(C6D6): δ18.34,18.77,24.43,26.78,32.52,56.73,112.78,116.67,122.62,125.59,126.10,126.51,1 26.61,126.86,128.14,128.69,129.03,129.28,132.20,134.71,136.41,137.64,139.79,141.75,155.92ppm.

[0302] - m / z calculated value ([M + ]C 25 H 24 N2) 352.4800. Measured value: 352.1942.

[0303] (ii) Preparation of transition metal compounds

[0304] [Chemical formula 1-3]

[0305]

[0306] At -78 ° C, MeMgBr (1.24 mL, 3.11 M ether solution) was added dropwise to a stirred HfCl4 suspension (0.300 g, 0.938 mmol) in toluene (8 mL). After stirring at a temperature of -40 ° C to -35 ° C for 1 hour, it was cooled to -78 ° C again. A solution (0.24 g, 0.94 mmol) of a ligand compound (0.366 g, 1.00 mmol) in toluene (4 mL) was added dropwise. The resulting solution was stirred at a controlled temperature of -40 ° C to -35 ° C for 2 hours, and then stirred at room temperature overnight. A vacuum line was used to remove the solvent, and the residue was extracted with toluene (50 mL). A dark brown powder (0.226 g, 47%) was obtained by pulverizing in hexane. 1 H NMR and 13 C NMR spectrum is shown in Figure 2 middle.

[0307] - 1 H NMR (C6D6): δ8.66(d,J=7.8Hz,H), 8.50(d,J=7.8Hz,H), 7.92(d,J=9.0Hz,H), 7.83(d,J=7.2Hz, H),7.76(d,J=8.4Hz,H),7.62(d,J=7.8Hz,H),7.40(td,J=7.2Hz,H),7.32(m,H),7.14(d,J=7.8H z,H),6.77(d,J=7.2Hz,H),4.02(m,H),2.80(m,H),2.62(dt,J=6.0Hz,H),2.55(m,H),1.88(m,H) ,1.72(m,H),1.09 and 1.04(d,J=6.6Hz,6H,CH(CH3)2),0.82(s,3H,HfCH3),0.81(s,3H,HfCH3)ppm.

[0308] - 13 C{ 1 H}NMR(C6D6): δ18.55,21.28,23.07,25.44,32.58,60.98,63.06,66.88,112.37,119.64,120.21,124.55,125.48,12 6.81,126.97,129.31,129.97,130.26,131.25,133.82,135.51,140.97,141.44,143.94,150.14,164.58,209.13ppm.

[0309] - Analytical calculation value (C 27 H 28HfN2): C, 58.01; H, 5.05; N, 5.01%.

[0310] - Found: C, 57.91; H, 5.01; N, 5.11%.

[0311] <Preparation of co-catalyst>

[0312] In a glove box, excess K + [B(C6F5)4] - (0.633 g, 0.881 mmol, assumed pure) and (C 18 H 37 )2N(H)Me] + [Cl] - The solution of (0.404 g, 0.705 mmol) was reacted for 1 hour. After filtering on diatomaceous earth, the solvent was removed using a vacuum line. The residue was dissolved in methylcyclohexane (4 mL) and then filtered on diatomaceous earth again. The solvent was removed to produce a yellow oily compound, which was used without further purification (0.797 g, 93%).

[0313] - 1 H NMR (C6D6): δ3.15(br,H,NH),1.97(m,2H,NCH2),1.80(m,H,NCH2),1.51(d,J=6.0Hz,3H,NCH3),1.45-1.29(m,48H),1.26( quintet,J=7.2Hz,4H),1.13(quintet,J=7.2Hz,4H),0.94(t,J=7.8Hz,6H),0.88(quintet,J=7.8Hz,4H),0.81(m,4H)ppm.

[0314] - 19 F NMR(C6D6): δ-132.09,-161.75,-165.98.

[0315] <Preparation of Organozinc Compounds>

[0316]

[0317] Borane dimethyl sulfide (1.6mL, 3.2mmol) was slowly introduced into triethylborane (0.6g) under stirring, and then reacted for 90 minutes. The mixture was slowly introduced into divinylbenzene (3.8g) dissolved in anhydrous ether (10mL) cooled to -20°C, and then stirred overnight. The solvent was removed with a vacuum pump, and then diethylzinc (0.8g) was added. The reaction was carried out at 0°C for 5 hours, and the triethylborane produced was removed by vacuum distillation. At 40°C, excess divinylbenzene and diethylzinc were removed by vacuum distillation. Methylcyclohexane (150mL) was added again to dissolve the product, and then the solid compound generated as a by-product was filtered and removed using diatomaceous earth to prepare the organic zinc compound represented by the above chemical formula.

[0318] <Preparation of polyolefin-polystyrene multi-block copolymer>

[0319] Preparation Example 1

[0320] A Parr reactor (1 gallon) was dried under vacuum at 120°C for 2 hours. A solution of Oc3Al (trioctylaluminum, 1466.4 mg, 1,000 μmol-Al) in methylcyclohexane (1,200 g) was added to the reactor. The mixture was stirred at 120°C for 1 hour using a heating jacket, and then the solution was removed using a cannula.

[0321] The reactor was filled with methylcyclohexane (1,200 g) containing Oc3Al (1,466.4 mg, 1,000 μmol-Al / 25 wt% hexane solution) as a scavenger and 1-hexene (560 g) as an olefin monomer, and the temperature was set to 90° C. A solution of an organozinc compound (3,100 μmol) in methylcyclohexane (3.85 g) was filled as a chain transfer agent, and then a solution containing [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] - A methylcyclohexane solution (1.68 g) of the activated transition metal compound (12.0 μmol-Hf) of Preparation Example 1 was prepared. The polymerization was carried out for 40 minutes while maintaining the pressure in the reactor at 25 bar by opening the valve of the ethylene tank. The temperature was adjusted within the range of 90 to 120° C., and the remaining ethylene gas was discharged.

[0322] When the temperature reached 90°C, Me3SiCH2Li·(PMDETA) solution prepared by mixing Me3SiCH2Li (244.8 mg, 2.6 mmol) and PMDETA (495.1 mg, 2.86 mmol) in methylcyclohexane (3.85 g) was added. The temperature was maintained at 90°C for 30 minutes during stirring, and then styrene (104.0 g) was injected. The temperature was adjusted in the range of 90 to 100°C using a heating jacket.

[0323] According to the aliquot 1 H NMR analysis confirmed that styrene was completely converted. After styrene was completely converted, 2-ethylhexanoic acid and ethanol were continuously injected. The obtained polymer block (300 g) was dried in a vacuum oven at 80° C. overnight to prepare a polyolefin-polystyrene multi-block copolymer.

[0324] Preparation Example 2

[0325] A polyolefin-polystyrene-based multi-block copolymer was prepared in the same manner as in Preparation Example 1, except that the amount of the organic zinc compound and the amount of styrene were different, as shown in Table 1 below.

[0326] Implementation of Preparation Examples 3 and 4

[0327] By repeating the same method as in Preparation Example 1, respective polyolefin-polystyrene-based multi-block copolymers were prepared.

[0328] Comparative Preparation Example 1

[0329] As commercially available SEBS, G1651 from Kraton Company was used.

[0330] Comparative Preparation Example 2

[0331] A polyolefin-polystyrene-based multi-block copolymer was prepared by the following method using a compound represented by the following chemical formula as a transition metal compound.

[0332] [Comparative Chemical Formula 1]

[0333]

[0334] A solution of trimethylaluminum (14.4 mg, 200 umol-Al) dissolved in methylcyclohexane (17 g) was injected into the high pressure reactor. The catalyst poisons in the high pressure reactor were purged at 100°C for 1 hour, and the solution was removed using a cannula.

[0335] The organozinc compound (49.1 mg, 150 μmol) was dissolved in methylcyclohexane (40 g) and introduced into the high pressure reactor, and the temperature was raised to 80° C. The transition metal compound and (C18 H 37 )N(Me)H + [B(C6F5)4] - The solution obtained by stirring 2 hours in benzene with 4.0 μmol of ethyl acetate (4.0 μmol) was diluted with a solution (1.0 g) obtained by dissolving trioctyl aluminum (50 μmol, 18.3 mg) in methylcyclohexane (15 g). Immediately after the catalyst solution was injected into the high-pressure reactor, an ethylene-propylene mixed gas was injected therein at a pressure of 20 bar (propylene 10 bar). The temperature was adjusted within the range of 95 to 115° C. Due to the consumption of the monomer, the pressure was gradually reduced, and the polymerization process was carried out at 45° C. for 60 minutes, and then the remaining gas was discharged.

[0336] Me3SiCH2Li (150 μmol, 14.1 mg) and PMDETA (150 μmol, 26 mg) were mixed with methylcyclohexane (1.0 g) and then injected into the reactor and stirred for another 30 minutes. The stirring temperature was maintained at 90°C to 100°C. Styrene (7.8 g) was injected into the high-pressure reactor and then reacted for 5 hours while maintaining the temperature at 90°C to 100°C to completely convert the styrene monomer. After the styrene monomer was completely converted, acetic acid and ethanol were continuously injected. The polymer was obtained and then dried overnight in a vacuum oven at 180°C.

[0337] [Table 1]

[0338]

[0339] Experimental Example 1

[0340] For the polyolefin-polystyrene-based multi-block copolymers of Preparative Examples 1 to 3 and Comparative Preparative Example 1, the physical properties of each of the copolymers were measured according to the following conditions and methods, and the results are shown in Table 2 below.

[0341] (1) Measurement of ethylene, α-olefin and styrene content

[0342] The measurement was performed by nuclear magnetic resonance (NMR). The measurement was performed using a Bruker 600MHz AVANCE III HD NMR device under the conditions of ns=16, d1=3s, solvent=TCE-d2, and 373K. 1 H NMR, and then calibrate the TCE-d2 solvent peak to 6.0 ppm. The CH3 of 1-propylene was confirmed at 1 ppm, and the CH3 related peak (triplet) of the butyl branch was confirmed by 1-hexene at around 0.96 ppm, thereby calculating the content. In addition, the aromatic peak around 6.5 to 7.5 ppm was used to calculate the content of styrene.

[0343] (2) Weight average molecular weight (Mw, g / mol) and polydispersity index (PDI)

[0344] The weight average molecular weight (Mw, g / mol) and number average molecular weight (Mn, g / mol) were determined by gel permeation chromatography (GPC), and the polydispersity index (PDI) was calculated by dividing the weight average molecular weight by the number average molecular weight.

[0345] - Column: PL Olexis

[0346] -Solvent: TCB (trichlorobenzene)

[0347] -Flow rate: 1.0ml / min

[0348] -Sample concentration: 1.0mg / ml

[0349] -Injection volume: 200μl

[0350] - Column temperature: 160℃

[0351] -Detector: Agilent high temperature RI detector

[0352] -Standard: Polystyrene

[0353] - Molecular weight was calculated by universal calibration using the Mark-Houwink equation (K = 40.8 × 10 -5 , α=0.7057)

[0354] (3) Calculation of constants A to D in equation 1

[0355] To calculate the values ​​of constants A to D, the GPC measurement data were fitted with a Gaussian function using Origin's nonlinear curve fitting.

[0356] also, Figure 3 A diagram showing the polyolefin-polystyrene-based multi-block copolymer obtained in Example 1 by Mathematical Formula 1 is shown.

[0357] [Table 2]

[0358]

[0359] Experimental Example 2

[0360] For the polyolefin-polystyrene-based multi-block copolymers of Preparative Examples 1 to 3 and Comparative Preparative Example 1, the peak values ​​of branch point carbon atoms and terminal carbon atoms of branches branched from the branch points are summarized and described in Table 3 below.

[0361] Specifically, using Bruker AVANCEIII 500MHz NMR as an instrument, about 50mg of the sample was added to 1.2ml of TCE-d2 (tetrachloroethane-d2) as a solvent and heated in a heating block at 100°C for 1 hour, during which time vortexing was performed 2 to 3 times. After confirming that the sample was melted uniformly, it was transferred to an MNR tube for measurement at 100°C. 13 C NMR spectroscopy.

[0362] [Table 3]

[0363] Branch point carbon atom The terminal carbon atom of the branch Preparation Example 1 38 14 Preparation Example 2 38 14 Preparation Example 3 38 14 Preparation Example 4 38 14 Comparative Preparation Example 1 34 11 Comparative Preparation Example 2 30 23

[0364] Experimental Example 3

[0365] (1) Tensile properties

[0366] Each specimen was prepared according to the tensile test method of ASTM D412, and its tensile strength, elongation and 300% modulus were measured.

[0367] [Table 4]

[0368] Tensile strength(MPa) Elongation(%) 300% modulus (MPa) Preparation Example 1 24.5 2,103 2.2 Preparation Example 2 22.9 1,904 2.1 Preparation Example 3 17.8 2,477 1.2 Preparation Example 4 24.1 1,959 1.9 Comparative Preparation Example 1 27.6 1,849 1.8 Comparative Preparation Example 2 4.3 490 2.3

[0369] As shown in Table 4, it was confirmed that the block copolymer of Implementation Preparation Example 1 exhibited excellent tensile properties in that tensile strength, elongation, and 300% modulus were all at predetermined levels, compared with the copolymer of Comparative Preparation Example 1 that did not satisfy all of the above conditions.

[0370] Example 1 - Preparation of Thermoplastic Resin Composition

[0371] To 50 parts by weight of the polyolefin-polystyrene multi-block copolymer prepared in the above-mentioned Example 1, 50 parts by weight of a high crystalline impact copolymer polypropylene (CB5230, a product of Korea Petrochemical Industry Co., Ltd.) having a melt index (230° C., 2.16 kg) of 30 g / 10 min was added, and solution blending was performed in xylene using a reactor to prepare a thermoplastic resin composition compound. At this time, the temperature was 200° C. to 230° C., the impeller speed was 400 rpm, and the blending time was 4 hours. After the blending was completed, the compound was recovered and then dried overnight in a vacuum oven at 100° C.

[0372] Examples 2 to 4 - Preparation of Thermoplastic Resin Compositions

[0373] A thermoplastic resin composition compound was prepared in the same manner as in Example 1, except that the polyolefin-polystyrene-based multi-block copolymer prepared in each of Preparation Examples 2 to 4 was used instead of the polyolefin-polystyrene-based multi-block copolymer prepared in Preparation Example 1.

[0374] Comparative Examples 1 and 2 - Preparation of Thermoplastic Resin Compositions

[0375] A thermoplastic resin composition compound was prepared in the same manner as in Example 1, except that the polyolefin-polystyrene-based multi-block copolymer prepared in Comparative Preparation Examples 1 and 2 was used instead of the polyolefin-polystyrene-based multi-block copolymer prepared in Comparative Preparation Example 1.

[0376] Experimental Example 4

[0377] 1) Low temperature impact strength

[0378] The low-temperature impact strength was measured according to ASTM D256 after aging the target by leaving it at a low temperature (-40°C) for 6 hours or more.

[0379] 2) Melt flow rate (MFR)

[0380] The measurement was conducted according to ASTM-D 1238 under the conditions of 230° C. and a load of 2.16 kg.

[0381] [Table 5]

[0382]

[0383] As can be seen in Table 5 above, it is confirmed that the thermoplastic resin compositions of Examples 1 to 4, which respectively contain the polyolefin-polystyrene multi-block copolymers of Preparation Examples 1 to 4, have excellent low-temperature impact strength and melt flow rate, and thus have significantly excellent overall physical properties compared to the thermoplastic resin compositions of Comparative Examples 1 and 2.

Claims

1. A thermoplastic resin composition, comprising: (1) Polypropylene; and (2) A polyolefin-polystyrene multi-block copolymer that satisfies the following conditions (a) to (c) as measured by gel permeation chromatography (GPC) and the following conditions under 500 MHz, tetrachloroethane-d2 and standard substance TMS: 13 The following conditions (d) were measured in C NMR spectroscopy: (a) having a weight average molecular weight of 144,188 to 200,000 g / mol, (b) having a molecular weight distribution of 1.6 to 2.2, (c) for the measurement result of gel permeation chromatography, the Gaussian function modeled by a graph with logMw as the x-axis and dw / dlogMw as the y-axis is represented by the following Mathematical Formula 1, wherein in the following Mathematical Formula 1, each constant value satisfies -0.05 < A < 0.06, 4.6 < B < 5.5, 0.9 < C < 1.1, and 0.5 < D < 0.9, (d) the polyolefin block contained in the polyolefin-polystyrene multi-block copolymer contains one or more branching points, wherein the carbon atoms of the branching points exhibit a peak at 36 ppm to 40 ppm, and the terminal carbon atoms of the branched chains branched from the branching points exhibit a peak at 13 ppm to 15 ppm, [Mathematical Formula 1] wherein, in the above Mathematical Formula 1, Mw represents the weight average molecular weight of the polyolefin-polystyrene multi-block copolymer, and w represents the concentration fraction of the polyolefin-polystyrene multi-block copolymer.

2. The thermoplastic resin composition according to claim 1, wherein Each constant value of the above Mathematical Formula 1 satisfies -0.04 < A < 0.040, 4.6 < B < 5.2, 0.91 < C < 1.09, and 0.6 < D < 0.

9.

3. The thermoplastic resin composition according to claim 1, wherein The polyolefin-polystyrene multi-block copolymer is one or more selected from the group consisting of polystyrene-poly(ethylene-co-propylene)-polystyrene block copolymer, polystyrene-poly(ethylene-co-1-butene)-polystyrene block copolymer, polystyrene-poly(ethylene-co-1-pentene)-polystyrene block copolymer, polystyrene-poly(ethylene-co-1-hexene)-polystyrene block copolymer, polystyrene-poly(ethylene-co-1-heptene)-polystyrene block copolymer, and polystyrene-poly(ethylene-co-1-octene)-polystyrene block copolymer.

4. The thermoplastic resin composition according to claim 1, wherein The polyolefin-polystyrene multi-block copolymer contains 10 wt% to 30 wt% of a polystyrene block.

5. The thermoplastic resin composition according to claim 1, wherein The polyolefin-polystyrene multi-block copolymer is prepared without hydrogenating the double bonds in the copolymer main chain.

6. The thermoplastic resin composition according to claim 1, wherein The weight ratio of the (1) polypropylene and the (2) polyolefin-polystyrene multi-block copolymer is 10:90 to 90:

10.

7. The thermoplastic resin composition according to claim 1, wherein The thermoplastic resin composition is a thermoplastic resin composition satisfying the following physical properties (A) to (C): (A) The room temperature impact strength is 3 kgf·m / m to 100 kgf·m / m, (B) The low temperature impact strength measured at -40°C is 2 kgf·m / m to 120 kgf·m / m, (C) The melt flow rate measured under the conditions of 230°C and 2.16 kg is 0.5 g / 10 min to 200 g / 10 min.

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