KR20220018942A - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition which comprises a polyolefin-polystyrene-based multi-block copolymer with a polystyrene chain attached to both terminals of polypropylene and polyolefin chains. The thermoplastic resin composition according to the present invention can exhibit a soft feeling and high restoring force while exhibiting high flow properties.

Description

Thermoplastic resin composition {THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a thermoplastic resin composition comprising polypropylene and a polyolefin-polystyrene-based multi-block copolymer having a structure in which polystyrene chains are attached to both terminals of the polyolefin chain.

Polypropylene, which is widely used as a grip for household goods or a material for interior and exterior parts for automobiles, has the advantage of excellent rigidity and molding processability, but has the disadvantage of weak impact strength. Thus, a polypropylene-based resin composition including an impact reinforcing material and an inorganic filler has been used. After ethylene-α-olefin copolymers synthesized by metallocene catalysts appeared, ethylene-α-olefin copolymers began to be used as impact modifiers for polypropylene. In the case of such a mixture composition of polypropylene and ethylene-α-olefin copolymer, the weak impact strength of polypropylene is supplemented and the low rigidity of the ethylene-α-olefin copolymer is supplemented.

However, when polypropylene is mixed with the ethylene-α-olefin copolymer, the soft feeling and restoring force of the ethylene-α-olefin copolymer are greatly reduced even if a small amount of polypropylene is added, and the ethylene-α- Even if the impact strength is supplemented by the addition of the olefin copolymer, there is still a limit to securing impact resistance according to various usage environments.

Accordingly, styrene-ethylene-butylene-styrene (SEBS), a styrenic thermoplastic elastomer, was used together with polypropylene for materials requiring soft feel and high resilience. However, SEBS is expensive, and there is a problem that flow marks or short shots occur by significantly lowering the fluidity of polypropylene.

Therefore, the development of a thermoplastic resin composition having a soft feeling and high restoring force while maintaining the high flow characteristics of polypropylene is still required.

Korean Patent Registration 10-1657925

The problem to be solved by the present invention is to provide a thermoplastic resin composition excellent in restoring force while having high flow characteristics.

In order to solve the above problems, the present invention provides (1) polypropylene, and (2) the amount of change in the loss tangent (tanδ) (y-axis) with respect to temperature (x-axis) obtained by dynamic mechanical analysis (DMA) In the graph showing , a thermoplastic resin composition comprising a polyolefin-polystyrene-based multi-block copolymer satisfying the following conditions (a) and (b) in a temperature range of -80 to 40°C is provided.

(a) the height of the tanδ peak is 0.45 to 0.60; and (b) a half width of the tanδ peak of 22.5 to 30.0°C.

The thermoplastic resin composition according to the present invention exhibits a soft feeling and high restoring force while exhibiting high flow characteristics.

1 shows ¹ H NMR and ¹³ C NMR spectra of a ligand compound used for preparing a polyolefin-polystyrene-based multi-block copolymer including a thermoplastic resin composition according to an embodiment of the present invention.
FIG. 2 shows ¹ H NMR and ¹³ C NMR spectra of a transition metal compound used for preparing a polyolefin-polystyrene-based multi-block copolymer including a thermoplastic resin composition according to an embodiment of the present invention.

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

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor appropriately defines the concept of the term in order to best describe his invention. Based on the principle that it can be done, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

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

The term "polymer," as used herein, refers to a polymer compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term homopolymer, which is commonly used to refer to polymers prepared from only one monomer, and the term interpolymer, as defined below.

The term "interpolymer," as used herein, refers to a polymer prepared by the polymerization of at least two different monomers. As such, the generic term interpolymer includes copolymers, which are commonly used to refer to polymers prepared from two different monomers, and polymers prepared from two or more different monomers.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention, (1) polypropylene, and (2) the amount of change in loss tangent (tanδ) (y-axis) with respect to temperature (x-axis) obtained by dynamic mechanical analysis (DMA) In the graph shown, the polyolefin-polystyrene-based multiblock copolymer satisfying the following conditions (a) and (b) in a temperature range of -80 to 40°C is included.

(a) the height of the tanδ peak is 0.45 to 0.60; and

(b) The half width of the tanδ peak is 22.5 to 30.0°C.

Hereinafter, each component will be described in detail.

(1) polypropylene

In the thermoplastic resin composition according to an embodiment of the present invention, the polypropylene may be specifically a polypropylene homopolymer or a copolymer of propylene and an alpha-olefin monomer, wherein the copolymer is alternating (alternating) ) or a random, or block copolymer.

The alpha-olefinic monomer may specifically be an aliphatic olefin having 2 to 12 carbon atoms, or 2 to 8 carbon atoms. More specifically, 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-aitocene, 4,4-dimethyl-1-pentene, 4,4- and diethyl-1-hexene or 3,4-dimethyl-1-hexene, and any one or a mixture of two or more thereof may be used.

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

In addition, the polypropylene has a melt index (MI) of 0.5 g/10min to 100 g/10min measured at 230°C and a load of 2.16 kg, specifically, the melt index (MI) is 1 g/10min to 90 g/ It can be 10 min. If the melt index of the polypropylene is out of the above range, there is a risk that a problem may occur during injection molding of the thermoplastic resin composition.

Specifically, in the thermoplastic resin composition according to an embodiment of the present invention, the polypropylene has a melt index (MI) of 0.5 g/10min to 100 g/10min, specifically 1 at 230°C and a load of 2.16 kg. It may be an impact copolymer of g/10min to 90 g/10min, and more specifically, it may be a propylene-ethylene impact copolymer, wherein the impact copolymer is 20% by weight based on the total weight of the polypropylene-based composite material. to 90 wt%, specifically 30 wt% to 70 wt%, more specifically 40 wt% to 60 wt% may be included. When the impact copolymer having such physical properties is included in the above-described content range as polypropylene, strength characteristics, particularly, strength characteristics at room temperature can be improved.

The above-mentioned impact copolymer may be prepared to satisfy the above-mentioned physical property requirements using a conventional polymer manufacturing reaction, or may be commercially obtained and used. Specific examples include SEETEC™ M1600 manufactured by LG Chem.

In addition, in the thermoplastic resin composition according to an embodiment of the present invention, the polypropylene has a DSC melting point in the range of 120 ° C to 160 ° C, and 230 ° C. according to ASTM-D 1238, measured at 2.16 kg load condition, and at least one random propylene copolymer having a melt flow rate (MFR) in the range of 5 g/10 min to 120 g/10 min, wherein the random propylene copolymer is 20 wt% to 90 wt%, based on the total weight of the polypropylene-based composite; Specifically, 30 wt% to 70 wt%, more specifically 40 wt% to 60 wt% may be included. When polypropylene having such physical properties is included in the above-described content range, mechanical strength of the thermoplastic resin composition such as hardness can be improved. The random propylene copolymer may be prepared to satisfy the above-described physical property requirements using a conventional polymer production reaction, or may be commercially obtained and used. Specific examples include Braskem™ PP R7021-50RNA from Braskem America Inc. or Formolene™ 7320A from Formosa Plastics Corporation.

(2) polyolefin-polystyrene-based multi-block copolymer

In the thermoplastic resin composition according to an embodiment of the present invention, the polyolefin-polystyrene-based multi-block copolymer has a loss tangent (tanδ) according to temperature (x-axis) obtained by dynamic mechanical analysis (DMA) ( In the graph showing the amount of change of the y-axis), it is characterized in that the following conditions (a) and (b) are satisfied in a temperature range of -80 to 40°C.

(a) the height of the tanδ peak is 0.45 to 0.60; and

(b) The half width of the tanδ peak is 22.5 to 30.0°C.

The loss tangent (tanδ) value means the ratio (E"/E') of the loss modulus (E") indicating the viscosity of the material to the storage modulus (E') indicating the elasticity of the material As such, it is used as an index for evaluating the viscoelastic properties of the copolymer.

With respect to the condition (a), the tanδ value according to temperature was measured for the polyolefin-polystyrene-based multi-block copolymer included in the thermoplastic resin composition according to an embodiment of the present invention, and the temperature was taken as the x-axis and tanδ was When represented by a graph on the y-axis, the height of the tanδ peak in the temperature range of -80 to 40°C is 0.45 to 0.60. Specifically, the height of the tanδ peak may be 0.45 or more, 0.47 or more, 0.48 or more, 0.50 or more, and may be 0.60 or less, 0.58 or less, 0.57 or less, and 0.55 or less.

The height of the tanδ peak indicates the y value when the tanδ value is the maximum in the range of -80 to 40°C on the x-axis, and in this case, the tanδ peak appears as one peak in the range of -50 to -30°C. can

When the height of the tanδ peak is too small, the loss modulus value compared to the storage modulus is small, so the degree of dispersing energy is lowered and there may be a problem that the impact strength is low, and when the height of the tanδ peak is excessive, the copolymer There may be a problem in that the flexural strength of the

With respect to the condition (b), the polyolefin-polystyrene-based multi-block copolymer has the above-described tanδ peak height, and the tanδ peak half width is 22.5 to 30.0°C. Specifically, the half width of the tanδ peak may be 22.5°C or more, 23.0°C or more, 24.0°C or more, 25.0°C or more, 25.5°C or more, 26.0°C or more, and 30.0°C or less, 29.0°C or less, 28.5°C or less.

The half width of the tanδ peak is T ₁ (low temperature) and T ₂ (high temperature), respectively, when the temperature at which the tanδ value is the half of the height of the tanδ peak defined in the condition (a) is T ₁ and T As it refers to the temperature range between ₂ T ₂ -T ₁ , it can be used as an index to interpret how the distribution of tanδ values appears according to the temperature change in the copolymer. Since the narrower the half width of the tanδ peak means faster transition from the glass phase to the rubber phase, the shorter the half width of the tanδ peak, the higher the impact strength, so it can be effectively used as an impact modifier.

When the range of the half width of the tanδ peak is excessive, the impact strength of the copolymer is lowered and there may be a problem in that a sufficient effect does not appear when used as an impact modifier.

As such, the polyolefin-polystyrene-based copolymer included in the thermoplastic resin composition according to an embodiment of the present invention has excellent impact strength by simultaneously satisfying the conditions (a) and (b), and is widely used as an impact modifier in various fields. can be used

The polyolefin-polystyrene-based multi-block copolymer may further satisfy the following conditions (c) and (d).

(c) a tanδ value of 0.10 to 0.30 at -10 to -30°C; and

(d) a tanδ value of 0.05 to 0.50 at 15 to 30°C.

The conditions (c) and (d) satisfy the change and distribution of the tanδ value according to the temperature as in the conditions (a) and (b) described above, respectively, and quantitatively express the tanδ value at low and high temperatures, respectively. , as the loss modulus value is large and the storage modulus value is small, the greater the tanδ value, the more efficiently the energy transferred from the impact when the copolymer is impacted can be effectively dispersed, and thus the degree of tolerance to the impact is excellent, which is excellent as an impact modifier It can mean that it can be used.

Regarding the condition (c), the tanδ value at -10 to -30°C may be 0.10 to 0.30, specifically 0.10 or more, 0.15 or more, 0.17 or more, and 0.30 or less, 0.25 or less, 0.21 or less. In addition, while satisfying the range of the tanδ value, a storage modulus E′ (storage modulus) value may be 1 to 200 MPa, and a loss modulus E″ (loss modulus) value may be 1 to 100 MPa.

In relation to the condition (d), the tanδ value at 15 to 30° C. may be 0.05 to 0.50, specifically 0.05 or more, 0.06 or more, and 0.50 or less, 0.40 or less, 0.30 or less, 0.20 or less, 0.10 or less. In addition, while satisfying the range of the tanδ value, the storage modulus E′ (storage modulus) value may be 0.1 to 50 MPa, and the loss modulus E″ (loss modulus) value may be 0.01 to 5 MPa.

As described above, the copolymer included in the thermoplastic resin composition according to an embodiment of the present invention satisfies the tanδ values of conditions (c) and (d), thereby satisfying a low temperature of -10 to -30°C and 15 to 30°C. It shows excellent impact strength at both high temperatures.

The polyolefin-polystyrene-based multiblock copolymer may have a weight average molecular weight of 40,000 to 300,000 g/mol, specifically 50,000 g/mol or more, 60,000 g/mol or more, 70,000 g/mol or more, and 250,000 g/mol or less. , 220,000 g/mol or less, and 210,000 g/mol or less.

In addition, the molecular weight distribution of the polyolefin-polystyrene-based multi-block copolymer is 1.0 to 3.0, specifically, may be 1.5 or more, 1.6 or more, and 3.0 or less, 2.5 or less, 2.0 or less, and 1.9 or less.

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 from the ratio (weight average molecular weight)/(number average molecular weight).

The polyolefin-polystyrene-based multi-block copolymer is 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- It may be at least one selected from the group consisting of poly(ethylene-co-1-octene)-polystyrene block copolymer.

In addition, the polyolefin 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 formula (a).

[Formula a]

In the above formula (a),

R ₁ is hydrogen; alkyl having 1 to 20 carbon atoms; alkyl having 1 to 20 carbon atoms substituted with silyl; arylalkyl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms substituted with silyl;

n may be an integer from 1 to 10,000.

In addition, according to an embodiment of the present invention, R ₁ Is hydrogen; It may be an alkyl having 3 to 20 carbon atoms.

In addition, according to an embodiment of the present invention, R ₁ Is hydrogen; Alternatively, it may be an alkyl having 3 to 12 carbon atoms, and specifically, R ₁ may be hydrogen or an alkyl having 4 to 12 carbon atoms.

In addition, n may be an integer of 10 to 10,000, specifically, may be an integer of 500 to 7,000.

On the other hand, in the formulas shown in the specification of the present invention, "*" represents a linking site as a terminal site of the repeating unit.

When the polyolefin block includes two or more types of repeating units represented by the formula (a), the polyolefin block may include the repeating units represented by the following formula (b).

[Formula b]

In the above formula (b),

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

0<p<1,

n' may be an integer from 1 to 10,000.

In addition, according to an embodiment of the present invention, the R ₁ ' and R ₁ " may each independently be hydrogen or an alkyl having 3 to 20 carbon atoms, and specifically, each independently hydrogen or an alkyl having 3 to 12 carbon atoms. and, more specifically, each independently may be hydrogen or an alkyl having 4 to 12 carbon atoms.

In addition, specifically, n' may be an integer of 10 to 10,000, and more specifically, an integer of 500 to 7,000.

According to an embodiment of the present invention, in Formula b, any one of R ₁ ' and R ₁ ″ may be hydrogen, and the other may be a substituent other than hydrogen among the aforementioned substituents.

That is, when the polyolefin block includes two or more kinds of repeating units represented by Formula (a), R ₁ is hydrogen and R ₁ is an alkyl having 1 to 20 carbon atoms other than hydrogen; alkyl having 1 to 20 carbon atoms substituted with silyl; arylalkyl having 7 to 20 carbon atoms; Alternatively, the silyl-substituted C7-20 arylalkyl structure may be randomly connected, specifically, a structure in which R ₁ is hydrogen and a structure in which R ₁ is an alkyl having 3 to 20 carbon atoms other than hydrogen. may be randomly connected.

In addition, more specifically, the polyolefin block may have a structure in which R ₁ is hydrogen and a structure in which R ₁ is an alkyl having 3 to 12 carbon atoms in Formula (a) are randomly connected, and more specifically, the polyolefin block is In Formula (a), the structure in which R ₁ is hydrogen and the structure in which R ₁ is alkyl having 4 to 12 carbon atoms may be randomly connected.

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

When the polyolefin block includes a structure in which R ₁ is hydrogen and a structure in which R ₁ is a substituent other than hydrogen in the above ranges in the above formula (a), the prepared block copolymer includes branches to an appropriate degree in the structure. , it has a high 300% modulus value and elongation at break value, thereby exhibiting excellent elastic properties, and exhibiting a wide molecular weight distribution with a high molecular weight to have excellent processability.

In addition, the first polystyrene block of the polyolefin-polystyrene-based multi-block copolymer included in the thermoplastic resin composition of the present invention may include at least one repeating unit represented by the following Chemical Formula c.

[Formula c]

In the above formula (c),

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

l is independently an integer from 10 to 1,000.

wherein R ₂ is phenyl; or phenyl unsubstituted or substituted with halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, or aryl having 6 to 12 carbon atoms, and R ₂ may be phenyl have.

The l is an integer of 10 to 1,000, and specifically may be an integer of 50 to 700, and when l is in the above range, the viscosity of the polyolefin-polystyrene block copolymer prepared by the manufacturing method of the present invention may have an appropriate level. have.

In particular, in the polyolefin-polystyrene-based multi-block copolymer included in the thermoplastic resin composition of the present invention, the polyolefin block including the repeating unit represented by the formula (a) and the first polystyrene including the repeating unit represented by the formula (c) The blocks may be combined with each other to form a complex block represented by the following Chemical Formula d.

[Formula d]

In the above formula d,

R ₁ is hydrogen; alkyl having 1 to 20 carbon atoms; alkyl having 1 to 20 carbon atoms substituted with silyl; arylalkyl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms substituted with silyl;

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

l is an integer from 10 to 1,000,

n is an integer from 1 to 10,000.

In addition, in Formula d, R ₁ , R ₂ , 1 and n are as defined in Formulas a and c, respectively.

In addition, when the polyolefin block includes the repeating unit represented by the formula (a), the composite block formed by bonding the first polystyrene block including the repeating unit represented by the formula (c) may be represented by the following formula (e).

[Formula e]

In Formula (e), R ₁ ′, R ₁ ″, p, 1 and n′ are the same as defined in Formula (a) or (c), respectively.

In addition, in one example of the present invention, when the polyolefin-polystyrene-based multi-block copolymer is prepared, the styrenic monomer forms a polyolefin block and, at the same time, the styrenic monomer is bonded to the organic zinc compound and polymerized to form a separate styrenic polymer block can form. In the present specification, the separate styrenic polymer block is referred to as a second polystyrene block. The second polystyrene block may include a repeating unit represented by the following Chemical Formula f.

[Formula f]

In the above formula f,

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

m is independently an integer from 10 to 1,000.

In addition, according to an embodiment of the present invention, R ₃ Is phenyl; or phenyl unsubstituted or substituted with halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, or aryl having 6 to 12 carbon atoms, and wherein R ₃ is phenylyl can

Wherein m is an integer of 10 to 1,000, specifically, may be an integer of 50 to 700.

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

Accordingly, the block copolymer composition may include a polyolefin block including at least one repeating unit represented by the following formula (a); A first polystyrene block including a repeating unit represented by the following formula (c); and a triblock copolymer including a second polystyrene block including a repeating unit represented by the following Chemical Formula f.

[Formula a]

[Formula c]

[Formula f]

In the above formula,

R ₁ is hydrogen; alkyl having 1 to 20 carbon atoms; alkyl having 1 to 20 carbon atoms substituted with silyl; arylalkyl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms substituted with silyl;

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

n is an integer from 10 to 10,000,

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

In addition, in the above formula, R ₁ , R ₂ , R ₃ , n, 1 and m are the same as defined in Formulas a, c and f, respectively.

Method for preparing polyolefin-polystyrene-based multi-block copolymer

The polyolefin-polystyrene-based multi-block copolymer preparation method (S1) forms a polyolefin block by polymerizing an olefinic monomer with an organic zinc compound as a chain transfer agent in the presence of a catalyst composition containing a transition metal compound represented by the following Chemical Formula 1 to do; and (S2) forming a polystyrene block by anionic polymerization of the polyolefin block and a styrenic monomer in the presence of an alkyl lithium compound containing a silicon atom and a triamine compound.

The polyolefin-polystyrene-based multi-block copolymer preparation method is as described below after forming a polyolefin chain using the transition metal compound represented by Formula 1, which is efficiently used for polymerization of olefinic monomers, as a catalyst, and then continuously using a styrene anion. By performing polymerization to form a polyolefin-polystyrene block, it is possible to form a polyolefin-polystyrene-based multiblock copolymer exhibiting a specific tanδ peak height and a half width of the tanδ peak.

Step (S1)

Step (S1) is a step of forming a polyolefin block by polymerizing an olefinic monomer by 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.

[Formula 1]

In Formula 1,

R ₁ to R ₁₁ are each independently 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,

Adjacent two or more of R ₁ to R ₁₁ 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,

X ₁ and X ₂ are each independently hydrogen; halogen; hydroxyl group; amino group; Psiogi; silyl group; cyano group; 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.

When the polymerization reaction is carried out in the presence of an excess of a chain transfer agent (e.g., (Et) ₂ Zn) relative to the catalyst, the olefin polymer chains cause rapid transalkylation between zinc (Zn) and hafnium (Hf) to uniformly from dialkylzinc It can grow to realize living polymerization, which is called coordinated chain transfer polymerization (CCTP). Conventionally used metallocene catalysts are impossible to carry out living polymerization through the β-elimination process, and even a few catalysts known to be applicable to CCTP only allow single polymerization of ethylene and ethylene and alpha-olefins. Since it was very difficult to proceed with the copolymerization of CCTP, it was very difficult to perform living polymerization through CCTP using a common transition metal compound as a catalyst and to prepare a block copolymer.

On the other hand, the hafnium compound represented by Formula 1 has a 1,2,3,4-tetrahydro-1,10-phenanthroline (1,2,3,4-tetrahydro-1,10-phenanthroline) skeleton and Hf- As a [N ^amido ,N,C ^aryl ]HfMe ₂ -type complex containing a C (aryl) bond, it exhibits excellent alpha-olefin mixing ability in the polymerization reaction of ethylene and alpha-olefin, especially depending on the content of the chain transfer agent The molecular weight of the olefin polymer or the content of alpha-olefin varies, indicating that the compound was successfully used for CCTP and that negligible β-elimination reaction occurred. That is, using the hafnium compound represented by Chemical Formula 1, it is possible to carry out living polymerization by performing CCTP copolymerization of ethylene and alpha-olefin monomers, and block copolymers having various block compositions can be successfully prepared.

In addition, it is possible to synthesize a polyolefin-polystyrene block copolymer by converting CCTP using the hafnium compound to an anionic styrene polymerization reaction. As such, the hafnium compound can be usefully used as a catalyst for the preparation of an olefin polymer, which is a unique feature that can be achieved with the novel structure of the hafnium compound represented by Formula 1 above.

Specifically, in Formula 1, R ₁ to R ₁₁ are each independently hydrogen; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 20 carbon atoms; Or it may be an aryl group having 6 to 20 carbon atoms, preferably R ₁ to R ₁₀ are hydrogen, and at the same time R ₁₁ is hydrogen; an alkyl group having 1 to 20 carbon atoms; Or it may be an aryl group having 6 to 20 carbon atoms, more preferably, R ₁ to R ₁₀ are hydrogen, and at the same time R ₁₁ is hydrogen; Or it may be an alkyl group having 1 to 20 carbon atoms.

Alternatively, in Formula 1, R _One to R ₁₁ are each independently hydrogen; an alkyl group having 1 to 20 carbon atoms; Or it may be an aryl group having 6 to 20 carbon atoms, in this case, R ₃ and R ₄ may be connected to each other to form an aromatic ring having 5 to 20 carbon atoms, such as a benzene ring, preferably R ₃ and R ₄ are each other connected to form a benzene ring, and at the same time R ₁₁ is an alkyl group having 1 to 20 carbon atoms; Or it may be an aryl group having 6 to 20 carbon atoms.

Alternatively, in Formula 1, R ₁ , R ₂ , and R ₅ to R ₁₀ are hydrogen, and R ₃ , R ₄ and R ₁₁ are each independently hydrogen; or an alkyl group having 1 to 20 carbon atoms, wherein R ₃ and R ₄ may be connected to each other to form an aromatic ring having 5 to 20 carbon atoms, such as a benzene ring.

Meanwhile, the X ₁ and X ₂ are each independently hydrogen; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 20 carbon atoms; Alternatively, it may be an aryl group having 6 to 20 carbon atoms, and preferably, each independently may be an alkyl group having 1 to 20 carbon atoms, and X ₁ and X ₂ may be the same as each other.

In the present invention, "alkyl" means a straight-chain or branched hydrocarbon residue.

In the present invention, "alkenyl" means a straight-chain or branched alkenyl group.

In the present invention, "aryl" preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.

In the present invention, "alkylaryl" means an aryl group substituted by the alkyl group.

In the present invention, "arylalkyl" refers to an alkyl group substituted by the aryl group.

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

In the present invention, "alkylamino" refers to an amino group substituted by the alkyl group, and includes, but is not limited to, a dimethylamino group, a diethylamino group, and the like.

In the present invention, unless otherwise stated, "hydrocarbyl" refers to a monovalent compound having 1 to 20 carbon atoms consisting only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl. means a hydrocarbon group.

More specifically, the hafnium compound represented by Formula 1 may be a hafnium compound represented by Formula 1a or 1b below:

[Formula 1a]

[Formula 1b]

In Formula 1a and Formula 1b,

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 arylalkyl group having 7 to 20 carbon atoms,

X ₁ and X ₂ are each independently hydrogen; halogen; hydroxyl group; amino group; Psiogi; silyl group; cyano group; 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.

The hafnium compound may be specifically represented by any one of the following Chemical Formulas 1-1 to 1-5, but is not limited thereto, and all hafnium compounds corresponding to Chemical Formula 1 are included in the present invention.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

The hafnium compound of the present invention may be prepared by reacting a compound represented by the following Chemical Formula 2 and a compound represented by Chemical Formula 3;

[Formula 2]

[Formula 3]

Hf(X ₁ X ₂ ) ₂

In the above formula,

Definitions of R ₁ to R _11, X ₁ and X ₂ are the same as described above.

Meanwhile, when preparing the hafnium compound represented by Chemical Formula 1, the step of preparing the ligand compound may be differently performed as follows depending on the structure of the finally prepared hafnium compound.

For example, when R ₃ and R ₄ do not form a ring with each other in the ligand compound and R ₁₁ is a hydrogen atom, the ligand compound is prepared by hydrogenation under a ruthenium catalyst as shown below, and then reacted with a compound represented by Formula 3 as a hafnium precursor. A hafnium compound can be prepared.

[Scheme 1]

In addition, in the case where R ₃ and R ₄ do not form a ring with each other in the ligand compound structure and R ₁₁ is a substituent other than a hydrogen atom, as shown in Scheme 2 below, R ₁₁ is first introduced using an organolithium compound and then under a ruthenium catalyst hydrogenation to prepare a ligand compound.

[Scheme 2]

In addition, when R ₃ and R ₄ are connected to each other in the ligand compound structure to form an aromatic ring having 5 to 20 carbon atoms and R ₁₁ is a substituent other than a hydrogen atom, R ₁₁ is first introduced using an organolithium compound as follows. Thereafter, in order to prevent hydrogenation of an aromatic ring such as a naphthyl group, hydrogenation under a Pd/C catalyst may be performed to prepare a ligand compound.

[Scheme 3]

That is, the hafnium compound may be prepared by introducing hafnium thereto after preparing a ligand compound through alkylation and hydrogenation under reagents and reaction conditions suitable for the compound that is a precursor of the ligand compound, and specific types of alkylation reagents, reaction temperature and A person skilled in the art may appropriately change the pressure and the like in consideration of the structure and experimental conditions of the final compound.

In the present invention, the organozinc compound is used as a chain transfer agent to induce chain transfer during preparation in a polymerization reaction to induce a copolymer to be prepared, and specifically, a compound represented by the following formula (4) can

[Formula 4]

In Formula 4,

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

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

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

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

Formula 4 may have a structure in which both ends of the formula are double bonds, for example, when B is arylene substituted with alkenyl, the arylene is connected to A and double bonds of alkenyl substituted with arylene A bond may be located at the outermost portion in Formula 4 above.

When the organozinc compound is reacted with one or more olefinic monomers in the presence of a catalyst composition, polymerization may occur while the olefinic monomer is inserted between zinc (Zn) and the organic group (A) of the organozinc compound. have.

The organic zinc compound may be mixed in an amount of 1 to 200 equivalents based on 1 equivalent of the transition metal compound of Formula 1, specifically, in an amount of 10 to 100 ? can be mixed.

Since the organic zinc compound does not contain impurities such as THF and a large amount of magnesium salt, it is possible to provide it with high purity, and thus it can be used as a chain transfer agent, and is advantageous for use in olefin polymerization.

The catalyst composition may further include a cocatalyst compound. In this case, the cocatalyst compound serves to activate the transition metal compound represented by Formula 1, and the cocatalyst may be one known in the art, for example, one selected from the following Chemical Formulas 5 to 7 as the cocatalyst. more can be used.

[Formula 5]

-[Al(R _a )-O] _m -

[Formula 6]

D(R _a ) ₃

[Formula 7]

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

In the above formula,

each R _a is 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 halogen,

m is an integer greater than or equal to 2,

D is aluminum or boron,

L is a neutral or cationic Lewis acid,

Z is a group 13 element,

A is each 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,

The substituent of A is halogen; hydrocarbyl having 1 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryloxy having 6 to 20 carbon atoms.

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

The compound represented by Formula 6 is not particularly limited, but preferred examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, and tri-s-butylaluminum. , tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like are included, and particularly preferred compounds are selected from trimethylaluminum, triethylaluminum, triisobutylaluminum.

Examples of the compound represented by Formula 7 include when Z is boron, for example, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate[(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [B(C) ₆ F ₅ ) ₄ ] ^- , dioctadecylmethylammonium tetrakis(phenyl)borate, dioctadecylmethylammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate tetrakis(phenyl)borate, tri Ethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tri Butylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilideium tetrapetylborate, N ,N-diethylanilideium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetra Phenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate , trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate , N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluoro phenylborate, triphenylphosphonium tetraphenylborate, triphenylcarbonium tetra(p-trifluoromethylphenyl)borate, triphenylcarbonium tetrapentafluorophenylborate, or a combination thereof, and Z is aluminum If , e.g. a tree Ethylammonium 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 tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, It may be triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, or a combination thereof, but is not limited thereto.

In particular, the cocatalyst used in the present invention may be a compound represented by Chemical Formula 7, specifically dioctadecylmethylammonium dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate.

In addition, the cocatalyst used in the present invention may be prepared in anhydrous hydrocarbon solvent. For example, the hydrocarbon solvent may be at least one selected from the group consisting of butane, pentane, neopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, xylene and ethylbenzene, but is limited thereto. and all hydrocarbon solvents available in the art can be used in anhydrous form.

In the present invention, when the cocatalyst is prepared under anhydrous hydrocarbon solvent, at least one peak appears in the range of 1.75 ppm to 1.90 ppm and the range of 1.90 ppm to 2.00 ppm, respectively, in ¹ H NMR spectrum. This indicates that the protons attached to the α-carbon adjacent to nitrogen, sulfur or phosphorus included in L show different peaks. For example, when the compound represented by Formula 1 is [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [B(C ₆ F ₅ ) ₄ ] ^- , in its ¹ H NMR spectrum, it is present in NC H ₂ Each of the two protons can give a different signal.

In addition, the hafnium compound represented by Formula 1 and the cocatalyst may be used in a supported form on a carrier. Silica or alumina may be used as the carrier, but is not limited thereto.

The olefin monomer introduced as a reactant in step (S1) is 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-eicocene, or a monomer formed of a mixture thereof, and the like. The said olefin monomer may be used individually by 1 type, and may be used in mixture of 2 or more types.

The step (S1) may be performed, for example, in a homogeneous solution state. In this case, as the solvent, a hydrocarbon solvent or an olefin monomer itself may be used as a medium. Examples of the hydrocarbon solvent include an aliphatic hydrocarbon solvent having 4 to 20 carbon atoms, specifically isobutane, hexane, cyclohexane, methylcyclohexane, and the like. The solvent may be used individually by 1 type, and may be used in mixture of 2 or more types.

The polymerization temperature of step (S1) may vary depending on the reaction material, reaction conditions, etc., and may be specifically carried out at 70 to 170 °C, specifically 80 to 150 °C, or 90 to 120 °C. Within the above range, while increasing the solubility of the polymer, it is possible to thermally stabilize the catalyst.

The polymerization in step (S1) may be carried out in a batch, semi-continuous or continuous mode, and may also be carried out in two or more steps having different reaction conditions.

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

Step (S2)

In the step (S2), anionic polymerization of the polyolefin block and a styrenic monomer in the presence of an alkyl lithium compound containing a silicon atom and a triamine compound successively to step (S1) to form a polystyrene block, This is a step for preparing a block copolymer.

In the step (S2), the styrenic monomer can be continuously inserted between the zinc-carbon bonds of (polyolefinyl) ₂ Zn included in the compound formed by the above step (S1), and at the same time in step (S1) The styrene group present in the terminal of the compound formed by the above may participate as a copolymerization site with a styrenic monomer to be connected to the polystyrene chain. In addition, the multi-block copolymer produced through the above process can be easily quenched by reacting the end groups with water, oxygen or organic acid, and thus is converted into an industrially useful polyolefin-polystyrene-based multi-block copolymer.

The styrenic monomer may be a styrene-based monomer having 6 to 20 carbon atoms. More specifically, it may be a styrene-based monomer including ethylene substituted with an aryl group having 6 to 20 carbon atoms, ethylene substituted with a phenyl group, and the like, for example, styrene.

The alkyl lithium compound including a silicon atom may be a compound represented by the following Chemical Formula 8.

[Formula 8]

(CH ₃ ) ₃ Si(CH ₂ )Li

The alkyl lithium compound containing such a silicon atom is a material widely used as an initiator of anionic polymerization, and it is easy to obtain and utilize in the present invention.

The triamine compound may be a compound represented by the following Chemical Formula 9.

[Formula 9]

The triamine compound is a compound used for the purpose of improving the reactivity as a base or as a nucleophile of the alkyl lithium compound by coordinating well with lithium, and it is easy to obtain and has a low unit price.

The present invention provides a polystyrene homopolymer, a polyolefin homopolymer, a polyolefin-polystyrene diblock copolymer by newly using the compounds of formulas 8 and 9 (eg, Me ₃ SiCH ₂ Li·(PMDETA)) as an initiator of step (S2). While suppressing the amount of coalescence, it is possible to maximize the production of the polyolefin-polystyrene-based multi-block copolymer, which is the object of the present invention.

The alkyl lithium compound including a silicon atom represented by Formula 8 and the triamine compound represented by Formula 9 may be mixed in an aliphatic hydrocarbon solvent, or alkyl lithium containing a silicon atom represented by Formula 8 in the reactor The compound and the triamine compound represented by Formula 9 may be sequentially added.

The anion polymerization temperature of step (S2) may vary depending on the reaction material, reaction conditions, etc., specifically, it may be carried out at 40 to 170 ℃, more specifically 60 to 150 ℃, or 90 to 100 ℃.

The anionic polymerization in step (S2) may be carried out in a batch, semi-continuous or continuous mode, and may also be carried out in two or more steps having different reaction conditions.

The anionic polymerization time of step (S2) may vary depending on the reaction material, reaction conditions, etc., but specifically may be 0.5 to 10 hours, 1 to 8 hours, 2 to 7 hours, or 4 to 6 hours. Within the above range, it is advantageous to convert the total amount of the styrene-based monomer to the multi-block copolymer.

As described above, in the production method of the present invention, polyolefin-polystyrene-based multiblock is grown through a method of continuously performing styrene anionic polymerization after growing a polyolefin chain through olefin polymerization using the organic zinc compound represented by Formula 4 above. A copolymer is prepared, and through this, a polyolefin-polystyrene-based multi-block copolymer having improved physical properties compared to the prior art and easy to use industrially can be efficiently prepared.

The method for producing a polyolefin-polystyrene-based multi-block copolymer according to an example of the present invention is different from the conventional method for producing a polyolefin-polystyrene-based multi-block copolymer, which is anionic polymerization of styrene and diene, followed by a two-step process of hydrogenation. According to another route, it is characterized in that it is prepared without hydrogenation reaction for double bonds in the main chain of the copolymer, and accordingly, the polyolefin-polystyrene-based multi-block copolymer included in the thermoplastic resin composition of the present invention is prepared for double bonds in the main chain. It is characterized in that it does not contain unsaturated bonds that are not saturated during the hydrogenation process.

On the other hand, the thermoplastic resin composition according to an embodiment of the present invention having the configuration as described above may include each component in an appropriate amount to satisfy its use and physical properties required accordingly. For example, in the present invention, the thermoplastic resin composition may include the (1) polypropylene and the (2) polyolefin-polystyrene-based multi-block copolymer in a weight ratio of 10:90 to 90:10, specifically 20: It may be included in a weight ratio of 80 to 80:20, and more specifically, it may be included in a weight ratio of 40:60 to 60:40.

When the content of the polyolefin-polystyrene-based multi-block copolymer included in the thermoplastic resin composition is too small, there is a risk of lowering impact strength, and when the content of the polyolefin-polystyrene-based multi-block copolymer is excessive, the thermoplastic resin composition liquidity may be reduced. The mixing ratio may be controlled in consideration of the remarkable physical properties of the polypropylene and polyolefin-polystyrene-based multi-block copolymer.

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

Specifically, the inorganic filler may be a powder-type filler, a flake-type filler, a fibrous filler, or a balloon-type filler, and any one or a mixture of two or more thereof may be used. Specifically, the powdery filler includes natural silicic acid or silicate such as fine powder talc, kaolinite, calcined clay, and sericite; carbonates such as precipitated calcium carbonate, ground calcium carbonate or magnesium carbonate; hydroxides such as aluminum hydroxide or magnesium hydroxide; oxides such as zinc oxide, magnesium oxide, or titanium oxide; synthetic silicic acids or silicates such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid or silicic anhydride; Silicon carbide etc. are mentioned. In addition, examples of the flake-type filler include mica. In addition, the fibrous filler may include basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fiber), or potassium titanate. In addition, the balloon-type filler may include a glass balloon. Among them, it may be talc.

In addition, the inorganic filler may be surface-treated to improve strength characteristics and molding processability of the thermoplastic resin composition.

Specifically, it may be one that has been physically or chemically surface treated using a surface treatment agent such as a silane coupling agent, higher fatty acid, fatty acid metal salt, unsaturated organic acid, organic titanate, resin acid, or polyethylene glycol.

In addition, the inorganic filler may have an average particle diameter (D ₅₀ ) of 1 μm to 20 μm, specifically 3 μm to 15 μm, and more specifically 5 μm to 10 μm. When the average particle diameter of the inorganic filler is too small, it is difficult to uniformly disperse when mixed with the polypropylene and polyolefin-polystyrene-based multi-block copolymer due to aggregation between the inorganic filler particles, and as a result, the effect of improving the mechanical properties of the thermoplastic resin composition may be insignificant. In addition, if the average particle diameter of the inorganic filler is excessive, there is a risk of deterioration of physical properties due to a decrease in the dispersibility of the inorganic filler itself.

In the present invention, the average particle diameter (D ₅₀ ) of the inorganic filler may be defined as a particle diameter based on 50% of the particle size distribution. In the present invention, the average particle diameter (D ₅₀ ) of the inorganic filler particles is, for example, a scanning electron microscope (scanning electron microscopy, SEM) or a field emission scanning electron microscope (field emission scanning electron microscopy, FE-SEM) using electrons, etc. It can be measured using microscopic observation or a laser diffraction method. When measuring by the laser diffraction method, more specifically, after dispersing inorganic filler particles in a dispersion medium, it is introduced into a commercially available laser diffraction particle size measuring device (eg Microtrac MT 3000), and 50 of the particle size distribution in the measuring device The average particle diameter (D ₅₀ ) on a % basis can be calculated.

The inorganic filler may be included in an amount of 0.1 parts by weight to 40 parts by weight based on 100 parts by weight of the thermoplastic resin composition. If 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 insignificant, and if it exceeds 40 parts by weight, the processability of the thermoplastic resin composition may decrease. More specifically, the inorganic filler may be included in an amount of 0.1 wt% to 20 wt% based on the total weight of the thermoplastic resin composition.

The thermoplastic resin composition according to an embodiment of the present invention that satisfies the composition and content conditions as described above may be prepared by adding polypropylene and optionally an inorganic filler to the polyolefin-polystyrene-based multi-block copolymer and then heat-treating it. can In this case, the type and content of the polypropylene are the same as described above.

The mixing process may be performed according to a conventional method. Specifically, the mixing may use a super mixer or a ribbon mixer.

In addition, in the mixing process, additives such as antioxidants, heat stabilizers, ultraviolet stabilizers, and antistatic agents may be further included as needed. may be optionally further used in

In addition, the heat treatment process may be performed at a temperature greater than or equal to the melting point of polypropylene and less than or equal to 210°C. The heat treatment process is a conventional twin-screw extruder (twin-screw extruder), single-screw extruder (single-screw extruder), roll mill (roll-mill), kneader (kneader) or Banbury mixer (banbury mixer) using various compounding machines, such as can be performed.

The thermoplastic resin composition according to an embodiment of the present invention prepared according to the manufacturing method as described above may have excellent elongation and tensile strength while exhibiting high fluidity.

Specifically, the thermoplastic resin composition may satisfy the following physical properties (A) to (D).

(A) Shore A hardness of 1 to 90,

(B) compression set is 0 to 80%,

(C) melt flow rate (MFR, 230 °C, 2.16 kg) 0.1 to 300 g / 10 min,

(D) melt flow rate (MFR, 230 °C, 5 kg) 0.1 to 500 g / 10 min.

(A) Shore A hardness may be 1 to 90, specifically 10 to 90, more specifically 20 to 90.

The shore A hardness may be measured according to ASTM D2240 standard.

(B) permanent compression set (compression set) may be 0 to 80%, specifically may be 1 to 80%, more specifically, may be 10% to 70%.

The compression set may be measured according to ASTM D-3574.

(C) the melt flow rate (MFR, 230 °C, 2.16 kg) may be 0.1 to 300 g/10min, specifically 0.2 to 200 g/10min, more specifically 0.5 to 100 g/10min have.

(D) melt flow rate (MFR, 230 ° C., 5 kg) may be 0.1 to 500 g/10 min, specifically 0.5 to 300 g/10 min, more specifically 2 to 150 g/10 min can

The melt flow rate was measured according to ASTM-D 1238 under conditions of 230° C., 2.16 kg load, and 230° C. and 5 kg load, respectively.

The thermoplastic resin composition according to an embodiment of the present invention is for blow molding, extrusion in various fields and uses such as materials for automobiles, electric wires, toys, textiles or medical materials, such as for various packaging, construction, and household products. It is useful for molding or injection molding, and in particular, it has excellent toughness and impact strength at room temperature as well as low temperature, as well as excellent physical properties such as heat resistance and rigidity, so it can be usefully used for interior and exterior parts of automobiles.

According to another embodiment of the present invention, there is provided a molded article and an automobile part manufactured using a thermoplastic resin composition satisfying the above-described physical property requirements.

Specifically, the molded article may be a blow molding molded article, an inflation molded article, a cast molded article, an extrusion laminate molded article, an extrusion molded article, an expanded molded article, an injection molded article, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric.

In addition, the automobile parts may be interior/exterior materials for automobiles, and the like.

Example

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.

<Preparation of transition metal compound>

Preparation Example 1

(i) Preparation of Ligand Compounds

To 2-naphthyl-1,10-phenanthroline (0.789 g, 2.58 mmol) in toluene (8 mL) at -10 °C was added isopropyllithium (0.45 mL, 0.36 mmol, 0.79 M in pentane) slowly. After stirring at room temperature for 3 hours, degassed H ₂ O (3 mL) was added. The aqueous layer was removed with a syringe under N ₂ . 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 N ₂ . After charging H ₂ gas to 5 bar, the mixture was stirred at room temperature for 12 hours. H ₂ gas was released and the catalyst residue was removed by filtration over Celite. The solvent was removed and the residue was purified by silica gel column chromatography using ethyl acetate/hexanes (1/3, v/v). A pale yellow sticky solid was obtained (0.085 g, 73%). ¹ H NMR and ¹³ C NMR spectra are shown in FIG. 1 .

- ¹ H NMR (C ₆ D ₆ ): δ 8.58 (d, J = 7.8 Hz, H), 7.75 (d, J = 9.0 Hz, H), 7.70 (d, J = 9.6 Hz, H), 7.66 ( d, J = 7.2 Hz, H), 7.63 (d, J = 6.6 Hz, H), 7.32 (m, 4H), 7.18 (d, J = 8.4 Hz, H), 6.99 (d, J = 7.8 Hz, H), 6.39(s, H, NH), 2.93(m, H), 2.79(m, H), 2.70(dt, J = 4.8 Hz, H), 1.70(m, H), 1.63(m, H) ), 1.47(m, H), 0.81(d, J = 7.2 Hz, 3H, CH(CH ₃ ) ₂ ), 0.76(d, J = 7.2 Hz, 3H, CH(CH ₃ ) ₂ ) ppm.

- ¹³ C{ ¹ H} NMR(C ₆ D ₆ ): δ 18.34, 18.77, 24.43, 26.78, 32.52, 56.73, 112.78, 116.67, 122.62, 125.59, 126.10, 126.51, 126.61, 126.86, 128.14, 128.69, 129.03, 129.28, 132.20, 134.71, 136.41, 137.64, 139.79, 141.75, 155.92 ppm.

- m/z calcd([M ⁺ ] C ₂₅ H ₂₄ N ₂ ) 352.4800. Found: 352.1942.

(ii) Preparation of transition metal compounds

[Formula 1-3]

To a stirred suspension (0.300 g, 0.938 mmol) of HfCl ₄ in toluene (8 mL) at -78 °C was added MeMgBr (1.24 mL, 3.11 M in diethyl ether) dropwise. After stirring for 1 hour at a temperature range of -40°C and -35°C, the solution was cooled back to -78°C. A solution (0.24 g, 0.94 mmol) of the ligand compound (0.366 g, 1.00 mmol) in toluene (4 mL) was added dropwise. The resulting solution was stirred at a controlled temperature within the range of -40°C and -35°C for 2 h, then at room temperature overnight. The solvent was removed using a vacuum line and the residue was extracted with toluene (50 mL). Trituration in hexane gave a dark brown powder (0.226 g, 47 %). ¹ H NMR and ¹³ C NMR spectra are shown in FIG. 2 .

- ¹ H NMR (C ₆ D ₆ ): δ 8.66 (d, J = 7.8 Hz, H), 8.50 (d, J = 7.8 Hz, H), 7.92 (d, J = 9.0 Hz, H), 7.83 ( d, J = 7.2 Hz, H), 7.76 (d, J = 8.4 Hz, H), 7.62 (d, J = 7.8 Hz, H), 7.40 (td, J = 7.2 Hz, H), 7.32 (m, H), 7.14 (d, J = 7.8 Hz, H), 6.77 (d, J = 7.2 Hz, H), 4.02 (m, H), 2.80 (m, H), 2.62 (dt, J = 6.0 Hz, H), 2.55(m, H), 1.88(m, H), 1.72(m, H), 1.09 and 1.04(d, J = 6.6 Hz, 6H, CH(CH ₃ ) ₂ ), 0.82(s, 3H) , HfCH ₃ ), 0.81(s, 3H, HfCH ₃ ) ppm.

- ¹³ C{ ¹ H} NMR(C ₆ D ₆ ): δ 18.55, 21.28, 23.07, 25.44, 32.58, 60.98, 63.06, 66.88, 112.37, 119.64, 120.21, 124.55, 125.48, 126.81, 126.97, 129.31, 129.97, 130.26, 131.25, 133.82, 135.51, 140.97, 141.44, 143.94, 150.14, 164.58, 209.13 ppm.

- Anal. Calcd. (C ₂₇ H ₂₈ HfN ₂ ): C, 58.01; H, 5.05; N, 5.01%.

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

<Preparation of co-catalyst>

Excess K ⁺ [B(C ₆ F ₅ ) ₄ ] ^- (0.633 g, 0.881 mmol, assumed pure) is [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ in toluene (anhydrous, 10 mL) A solution of [Cl] ^- (0.404 g, 0.705 mmol) was reacted for 1 hour at room temperature in a glove box. After filtration over Celite, the solvent was removed using a vacuum line. The residue was dissolved in methylcyclohexane (4 mL) and filtered again over Celite. Removal of the solvent gave a yellow oily compound, which was used without further purification (0.797 g, 93 %).

- ¹ H NMR (C ₆ D ₆ ): δ 3.15 (br, H, NH), 1.97 (m, 2H, NCH ₂ ), 1.80 (m, H, NCH ₂ ), 1.51 (d, J = 6.0 Hz, 3H, NCH ₃ ), 1.45-1.29 (m, 48H), 1.26 (quintet, J = 7.2 Hz, 4H), 1.13 (quintet, J = 7.2 Hz, 4H), 0.94 (t, J = 7.8 Hz, 6H) , 0.88 (quintet, J = 7.8 Hz, 4H), 0.81 (m, 4H) ppm.

- ¹⁹ F NMR (C ₆ D ₆ ): δ -132.09, -161.75, -165.98.

<Preparation of organic zinc compound>

Borane dimethyl sulfide (1.6 mL, 3.2 mmol) was slowly added to triethylborane (0.6 g) under stirring, followed by reaction for 90 minutes. It was slowly added to divinylbenzene (3.8 g) dissolved in anhydrous diethyl ether (10 mL) cooled to -20 °C, and then stirred overnight. After removing the solvent with a vacuum pump, diethyl zinc (0.8 g) was added. The reaction proceeded while removing triethylborane produced through distillation under reduced pressure at 0° C. for 5 hours. Excess divinylbenzene and diethyl zinc were removed by distillation under reduced pressure at 40°C. Methylcyclohexane (150 mL) was added to dissolve the product again, and the solid compound produced as a by-product was filtered off using Celite to prepare an organozinc compound represented by the above formula.

<Production of polyolefin-polystyrene-based multi-block copolymer>

Example Preparation Example 1

The Parr reactor (1 gallon) was vacuum dried at 120° C. for 2 hours. A solution of Oc ₃ Al (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, then the solution was removed using a cannula.

After the reactor was charged with methylcyclohexane (600 g) containing Oc ₃ Al (715.6 mg, 488 μmol-Al / 25 wt % in hexane) as a scavenger and 1-hexene (280 g) as an olefin monomer, the temperature was It was set at 90°C. A solution of the above organozinc compound (3,000 μmol) in methylcyclohexane (3.85 g) as chain transfer agent was charged followed by [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [B(C ₆ F) in methylcyclohexane ₅ ) ₄ ] ^- (9.0 μmol) methylcyclohexane solution (1.68 g) containing the transition metal compound (9.0 μmol-Hf) of Preparation Example 1 was injected. Polymerization was carried out for 40 minutes while opening the valve of the ethylene tank and maintaining the pressure in the reactor to be 25 bar. The temperature was controlled within the range of 90 to 120 °C, and the remaining ethylene gas was discharged.

When the temperature reached 90° C., Me ₃ SiCH ₂ Li (244.8 mg, 2.6 mmol) and PMDETA (495.1 mg, 2.86 mmol) were mixed in methylcyclohexane (3.85 g) to prepare Me ₃ SiCH ₂ Li·(PMDETA) ) solution was added. After maintaining the temperature at 90° C. for 30 minutes while stirring, styrene (88.0 g) was injected. The temperature was controlled in the range of 90 to 100°C using a heating jacket.

¹ H NMR analysis of an aliquot confirmed complete conversion of styrene. After complete conversion of styrene, 2-ethylhexanoic acid and ethanol were continuously injected. The resulting polymer mass (300 g) was dried in a vacuum oven at 80° C. overnight.

Example Preparation 2

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 changed as shown in Table 1 below.

Comparative Preparation Example 1

As a commercially obtained SEBS, G1651 from Kraton was used.

Comparative Preparation Example 2

Using the compound represented by the following formula as a transition metal compound, it was prepared by the following method.

[Comparative formula 1]

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

The organozinc compound (49.1 mg, 150 μmol) was dissolved in methylcyclohexane (40 g) in a high-pressure reactor, and the temperature was raised to 80°C. A solution of the transition metal compound (C ₁₈ H ₃₇ )N(Me)H ⁺ [B(C ₆ F ₅ ) ₄ ] ^- (4.0 μmol) in benzene was stirred for 2 hours in trioctylaluminum (50 μmol, 18.3) mg) was diluted with a solution (1.0 g) in methylcyclohexane (15 g). After the catalyst solution was injected into the high-pressure reactor, an ethylene-propylene mixed gas was immediately injected at a pressure of 20 bar (propylene 10 bar). The temperature was controlled in the range of 95-115 °C. The pressure was gradually reduced due to the consumption of the monomer, and the polymerization process was performed at 45° C. for 60 minutes, and then the remaining gas was discharged.

Me ₃ SiCH ₂ Li (150 μmol, 14.1 mg) and PMDETA (150 μmol, 26 mg) were mixed with methylcyclohexane (1.0 g) and injected into the reactor, followed by stirring for 30 minutes. The stirring temperature was maintained from 90°C to 100°C. Styrene (7.8 g) was injected into the high-pressure reactor and reacted for 5 hours while maintaining the temperature between 90° C. and 100° C. to convert all of the styrene monomer. After complete conversion of the styrene monomer, acetic acid and ethanol were continuously injected. After the polymer was obtained, it was dried overnight in a vacuum oven at 180°C.

Catalyst type Catalyst dosage
(umol) cocatalyst
(umol) Zn
(umol) Alpha-olefins styrene
(g) Kinds Dosage (g) Example Preparation Example 1 Formula 1-3 12.0 12.0 3,720 1-hexene 560 109 Example Preparation 2 Formula 1-3 12.0 12.0 3,100 1-hexene 560 104 Comparative Preparation Example 1 Commercial SEBS (G1651) Comparative Preparation Example 2 Comparative formula 1 4.0 4.0 150 propylene 10 bar 7.8

Experimental Example 1

For the polyolefin-polystyrene-based multi-block copolymers of Preparation Examples 1 and 2 and Comparative Preparation Examples 1 and 2, the physical properties of each copolymer were measured according to the following conditions and methods, and the results are shown in Table 2.

(1) storage modulus (E'), loss modulus (E") and tanδ values

Using a DMA (Dynamic mechanical analysis) instrument, the temperature was increased from -90°C to 100°C at a rate of 5°C per minute at a frequency of 1 Hz and a strain of 0.1%.

(2) the height of the tanδ peak

In the graph showing the amount of change in the loss tangent (tanδ) (y-axis) according to the temperature (x-axis) obtained by dynamic mechanical analysis (DMA), when the tanδ value is maximum in the temperature range of -80 to 40°C The y value was measured.

(3) Half width of the tanδ peak

The width (T ₂ -T ₁ ) between T ₁ and T ₂ was calculated as the temperature having a half value of the height of the tanδ peak as T ₁ and T ₂ , respectively.

-20℃ 23℃ tanδ peak height Half width of tanδ peak E' (MPa) E" (MPa) tanδ E' (MPa) E" (MPa) tanδ Example Preparation Example 1 6.05 1.05 0.17 1.16 0.07 0.06 0.50 26.4 Example Preparation 2 19.43 3.54 0.18 5.49 0.44 0.08 0.57 25.9 Comparative Preparation Example 1 68.92 10.13 0.15 23.05 1.42 0.06 0.41 21.1 Comparative Preparation Example 2 93.12 15.72 0.17 22.42 2.20 0.10 0.27 50.2

Experimental Example 2

(1) weight average molecular weight (Mw, g/mol) and molecular weight distribution (polydispersity index, PDI)

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

- Column: PL Olexis

- Solvent: TCB (trichlorobenzene)

- Flow rate: 1.0 ml/min

- Sample concentration: 1.0 mg/ml

- Injection volume: 200 μl

- Column temperature: 160℃

- Detector: Agilent High Temperature RI detector

- Standard: Polystyrene

- Using Mark-Houwink equation (K = 40.8 x 10 ^-5 , α=0.7057), calculate molecular weight with Universal Calibration

(2) Impact strength

Using a twin-screw extruder, 90% by weight of the polypropylene homopolymer and 10% by weight of the copolymer of Preparation Example or Comparative Preparation Example were mixed, and this was prepared as a specimen.

Impact strength (Notched Izod, J/m) was measured at -30°C and 25°C, respectively, according to standard measurement ASTM D256.

GPC -30℃ Impact strength (J/m) 25℃ Impact strength (J/m) Mw (g/mol) PDI Example Preparation Example 1 160,889 1.77 24.30 NB (no break) Example Preparation 2 180,236 1.79 32.05 NB (no break) Comparative Preparation Example 1 139,300 1.10 20.04 NB (no break) Comparative Preparation Example 2 93,075 1.73 12.32 NB (no break)

Example 1 - Preparation of thermoplastic resin composition

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

Example 2 - Preparation of thermoplastic resin composition

The same as in Example 1, except that the content of the polyolefin-polystyrene-based multi-block copolymer prepared in Example 1 and the content of the high crystallinity impact copolymer polypropylene were respectively 80 parts by weight and 20 parts by weight, respectively. A thermoplastic resin composition compound was prepared by the method.

Example 3 - Preparation of thermoplastic resin composition

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

Example 4 - Preparation of thermoplastic resin composition

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

Comparative Example 1 - Preparation of thermoplastic resin composition

The thermoplastic resin composition in the same manner as in Example 1, except that the polyolefin-polystyrene-based multi-block copolymer of Comparative Preparation Example 1 was used instead of the polyolefin-polystyrene-based multi-block copolymer prepared in Preparation Example 1 compound was prepared.

Comparative Example 2 - Preparation of thermoplastic resin composition

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

Comparative Example 3 - Preparation of thermoplastic resin composition

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

Comparative Example 4 - Preparation of thermoplastic resin composition

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

Experimental Example 3

For the thermoplastic resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4, physical properties were measured according to the following conditions and methods, and the results are shown in Table 4.

(1) Determination of contents of ethylene, alpha-olefin and styrene

The copolymers of Preparation Example 1 and Comparative Preparation Example 1 were measured through NMR. ¹ H NMR was measured at ns=16, d1=3s, solvent=TCE-d2, 373K using Bruker 600MHz AVANCE III HD NMR equipment, and the TCE-d2 solvent peak was corrected to 6.0 ppm, and 1- The content of CH ₃ of propylene was calculated after confirming the CH ₃ related peak (triplet) of the butyl branch with 1-hexene near 0.96 ppm. In addition, the content of styrene was calculated as an aromatic peak near 6.5 to 7.5 ppm.

(2) Measurement of hardness (shore A)

Hardness was measured according to ASTM D2240 standard using TECLOCK's GC610 STAND for Durometer and Mitutoyo's Shore Durometer Type A.

(3) compression set

Examples 1 and 2 and Comparative Examples 1 and 2, using the thermoplastic resin composition of 12.5 ± 0.5 mm thickness, diameter 29 ± 0.5 mm of the specimen prepared in the form of a cylinder was measured according to ASTM D-395. Put the test piece between two parallel metal plates, insert a spacer with a thickness of 9.5±0.02 mm, and compress it at room temperature (20±0.5℃). The thickness was measured after leaving it for 30 minutes. In the same test example, three specimens were used, and the permanent compression set was calculated by the following formula (1).

[Formula 1]

Permanent compression set (%)=[(t ₀ -t _f )/(t ₀ -t _s )]×100

t ₀ is the initial thickness of the specimen, t _f is the thickness of the specimen when cooled after heat treatment, and t _s is the thickness of the spacer.

(4) melt flow rate (MFR)

According to ASTM-D 1238, it was measured at 230℃, 2.16kg load condition and 230℃, 5kg load condition, respectively.

As can be seen in Table 4, Examples 1 and 3 having the same multi-block copolymer content, Comparative Examples 1 and 3, Examples 2 and 4, and Comparative Examples 2 and 4 are compared, respectively, in Example Preparation Example 1 Or 2, the polyolefin-polystyrene-based multi-block copolymer of Examples 1 to 4, respectively, comprising the thermoplastic resin composition of Comparative Preparation Examples 1 or 2, the polyolefin-polystyrene-based multi-block copolymer of Comparative Examples 1 to 4, respectively Compared to the thermoplastic resin composition, it exhibited a significantly higher MFR value and a lower compression set value, confirming that it exhibits excellent restoring force with excellent fluidity. In addition, it was confirmed that the thermoplastic resin compositions of Examples 1 to 4 exhibited slightly lower hardness than the thermoplastic resin compositions of Comparative Examples 1 to 4, but still maintained a high hardness value. Through this, it was confirmed that the thermoplastic resin compositions of Examples 1 to 4 exhibited high restoring force with high flow characteristics while maintaining high hardness.

Claims (13)

(1) polypropylene, and
(2) In a graph showing the amount of change in the loss tangent (tanδ) (y-axis) according to the temperature (x-axis) obtained by dynamic mechanical analysis (DMA), the following (a) ) and (b) a thermoplastic resin composition comprising a polyolefin-polystyrene-based multi-block copolymer satisfying the conditions:
(a) the height of the tanδ peak is 0.45 to 0.60; and
(b) The half width of the tanδ peak is 22.5 to 30.0°C.
The method of claim 1,
In the condition (a), the tanδ peak appears as one peak in the range of -50 to -30°C.
The method of claim 1,
In the condition (b), the half width of the tanδ peak is 23.0 to 29.0° C. of the thermoplastic resin composition.
The method of claim 1,
The polyolefin-polystyrene-based multi-block copolymer is a thermoplastic resin composition that further satisfies the following conditions (c) and (d):
(c) a tanδ value of 0.10 to 0.30 at -10 to -30°C; and
(d) The tanδ value at 15 to 30 ℃ is 0.05 to 0.50.
5. The method of claim 4,
The polyolefin-polystyrene-based multi-block copolymer has a storage modulus E' (storage modulus) value of 1 to 200 MPa and a loss modulus E" (loss modulus) value at -10 to -30 ° C. Thermoplastic resin composition of 1 to 100 MPa .
5. The method of claim 4,
The polyolefin-polystyrene-based multi-block copolymer has a storage modulus E' (storage modulus) value of 0.1 to 50 MPa and a loss modulus E" (loss modulus) value of 0.01 to 5 MPa at 15 to 30° C. A thermoplastic resin composition.
The method of claim 1,
The polyolefin-polystyrene-based multi-block copolymer is a thermoplastic resin composition having a weight average molecular weight of 40,000 to 300,000 g/mol.
The method of claim 1,
The polyolefin-polystyrene-based multi-block copolymer is a thermoplastic resin composition having a molecular weight distribution of 1.0 to 3.0.
The method of claim 1,
The polyolefin-polystyrene-based multi-block copolymer is 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- At least one thermoplastic resin composition selected from the group consisting of poly(ethylene-co-1-octene)-polystyrene block copolymers.
The method of claim 1,
The polyolefin-polystyrene-based multi-block copolymer is a thermoplastic resin composition comprising 10% to 30% by weight of a polystyrene-based block.
The method of claim 1,
The polyolefin-polystyrene-based multi-block copolymer is a thermoplastic resin composition, characterized in that it is prepared without hydrogenation reaction for double bonds in the copolymer main chain.
The method of claim 1,
The (1) polypropylene and the polyolefin-polystyrene-based multi-block copolymer have a weight ratio of 10:90 to 90:10 in a thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is a thermoplastic resin composition satisfying the physical properties of the following (A) to (D):
(A) Shore A hardness of 1 to 90,
(B) compression set is 0 to 80%,
(C) melt flow rate (MFR, 230 °C, 2.16 kg) 0.1 to 300 g / 10 min;
(D) melt flow rate (MFR, 230 °C, 5 kg) 0.1 to 500 g / 10 min.

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