TW202222957A - Thermoplastic resin composition - Google Patents

Abstract

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

Description

Thermoplastic resin composition

This case claims the rights of Korean Patent Application No. 10-2020-0095282 filed with the Korean Intellectual Property Office on July 30, 2020, the disclosure of which is incorporated herein by reference in its entirety.

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

Polypropylene has excellent rigidity and molding processability, and thus is widely used as a material for interior and exterior parts of automobiles, but disadvantageously is weak in impact strength. Therefore, in general, as a composition for automobile interior and exterior parts, polypropylene-based materials containing polypropylene (PP) as a main component and impact resistant reinforcing materials and inorganic fillers have been used resin composition.

Generally, as a material for automobile interior and exterior materials (especially for bumper covers), ethylene propylene rubber (EPR) or ethylene propylene diene rubber (EPDM) is mainly used as most Impact-resistant reinforcement material in resin compositions mainly composed of polypropylene. Due to the introduction of ethylene-α-olefin copolymers synthesized by metallocene catalysts, ethylene-α-olefin copolymers have been used as impact-resistant reinforcing materials. Polypropylene-based resin composition using ethylene-α-olefin copolymer has balanced physical properties such as impact strength, modulus of elasticity, flexural rigidity, etc., and has good moldability (moldability), and also cheap. However, the polypropylene-based resin composition using the ethylene-α-olefin copolymer has limitations in securing impact resistance depending on various usage environments.

In addition, styrene-ethylene-butylene-styrene (SEBS), which is a styrene-based thermoplastic elastomer (thermoplastic elastic body), has also been used in polypropylene-based resin compositions, but the disadvantage is that SEBS is expensive And the fluidity of polypropylene is significantly deteriorated.

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

prior technical documents

[patent document]

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

technical problem

One aspect of the present invention provides a thermoplastic resin composition having high flow properties but exhibiting excellent mechanical strength and significantly improved impact strength properties. Technical solutions

According to one aspect of the present invention, there is provided a thermoplastic resin composition comprising: (1) polypropylene, and (2) a polyolefin-polystyrene-based multi-block copolymer, which satisfies the requirements of a gel permeable layer The following conditions (a) to (c) measured by Gel Permeation Chromatography (GPC) and at ¹³ C NMR (500 MHz, tetrachloroethane-d2 (tetrachloroethane-d2), standard material (TMS)) Spectrum of the following condition (d).

(a) a weight average molecular weight of 50,000 to 300,000 g/mol,

(b) a molecular weight distribution of 1.5 to 3.0,

(c) For GPC measurement results, a Gaussian function constructed from a graph with logMw as the x-axis and dw/dlogMw as the y-axis is represented by the following equation 1, where in the following equation 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

(d) The polyolefin block (polyolefin block) contained in the polyolefin-polystyrene-based multi-block copolymer comprises one or more branching points, wherein the The carbon atoms exhibited a peak of 36 to 40 ppm, while the terminal carbon atoms of the branched chains branched from the branch point exhibited a peak of 13 to 15 ppm.

[Equation 1]

(In Equation 1 above, Mw represents the weight average molecular weight of the polyolefin-polystyrene-based multi-block copolymer.) Advantageous Effects

The thermoplastic resin composition according to the present invention has significantly improved impact strength properties and high flow properties, and thus can exhibit excellent molding processability.

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

It is to be understood that words or terms used in the description of the invention and the scope of the claims should not be construed as limited to having the meanings defined in common dictionaries. Further understand that, based on the principle that the inventor can properly define the meaning of words or terms to best explain the present invention, these words or terms should be interpreted as having meanings consistent with their meanings in the relevant technical content and the technical concept of the present invention .

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

As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers, whether of the same or different species. Thus, the generic term "polymer" encompasses the term "homopolymer", which is commonly used to refer to polymers prepared from only one monomer, as well as the term "interpolymer" as defined below.

As used herein, the term "interpolymer" refers to a polymer prepared by polymerizing at least two different kinds of monomers. Thus, the generic term "interpolymer" encompasses the term "copolymer", which is generally used to refer to polymers prepared from two different kinds of monomers, as well as those prepared from two or more different kinds of monomers. the term "polymer".

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention comprises (1) polypropylene, and (2) a polyolefin-polystyrene-based multi-block copolymer, which is a polyolefin-polystyrene-based multi-block copolymer. The following conditions (a) to (c) as measured by gel permeation chromatography (GPC) and the following condition (d) ^at13C NMR (500 MHz, tetrachloroethane-d2, standard material TMS) spectrum were satisfied.

(a) a weight average molecular weight of 50,000 to 300,000 g/mol,

(b) a molecular weight distribution of 1.5 to 3.0,

(c) For GPC measurement results, a Gaussian function constructed from a graph with logMw as the x-axis and dw/dlogMw as the y-axis is represented by the following equation 1, where in the following equation 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

(d) The polyolefin block (polyolefin block) contained in the polyolefin-polystyrene-based multi-block copolymer comprises one or more branching points, wherein the Carbon atoms exhibit a peak of 36 to 40 ppm, while terminal carbon atoms of branched chains branched from this branch point exhibit a peak of 13 to 15 ppm.

[Equation 1]

(In Equation 1 above, Mw represents the weight average molecular weight of the polyolefin-polystyrene-based multi-block copolymer.)

Hereinafter, each constituent component will be described in detail.

(1) Polypropylene

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 alpha-olefin monomer, wherein, The copolymers can be alternating or random copolymers, or block copolymers.

Specifically, the α-olefin-based monomer may 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-tetradecene), 1-hexadecene, 1-eicosene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1 -hexene, or 3,4-dimethyl-1-hexene, etc., any one of them or a mixture of two or more of them can be used.

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

Additionally, the polypropylene may have a melt index (MI) of 0.5 g/10 min to 100 g/10 min measured at 230°C and a 2.16 kg load. Specifically, the melt index (MI) can be from 1 g/10 min to 90 g/10 min. When the melt index of polypropylene is outside the above range, problems 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 may have a measurement of 0.5 g/10 min to 100 g/10 min, especially 1 g at 230° C. and a load of 2.16 kg The impact copolymer having a melt index (MI) from 10 min to 90 g/10 min, or, more specifically, may be a polypropylene-ethylene impact copolymer. When the impact-resistant copolymer having the above-mentioned physical properties is contained within the above-mentioned content range as polypropylene, the impact-strength property can be improved, especially, the room-temperature strength property can be improved.

The content of impact copolymer (impact copolymer), based on the total weight of the thermoplastic resin composition, may be 10 wt% to 90 wt%, particularly 20 wt% to 80 wt%, more particularly 40 wt% to 40 wt% 60 wt%.

Impact copolymers may be prepared using typical polymer preparation reactions to meet the above physical property requirements, or may be commercially available and used. Specific examples thereof may include SEETEC™ M1600 (a product of LG Chem) and the like.

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

When the polypropylene having the above-mentioned physical properties is contained within the above-mentioned content range, the mechanical strength such as hardness of the thermoplastic resin composition can be improved.

The content of the random propylene copolymer may be 10 wt% to 90 wt%, particularly 20 wt% to 80 wt%, more particularly 40 wt% to 60 wt%, based on the total weight of the thermoplastic resin composition.

Random propylene copolymers may be prepared using typical polymer preparation reactions to meet the above physical property requirements, or may be commercially available and used. Specific examples thereof may include Braskem™ PP R7021-50RNA of Braskem America Inc., Formolene™ 7320A of Formosa Plastics Corporation of USA, and the like.

(2) Multi-block copolymers based on polyolefin-polystyrene

In the thermoplastic resin composition according to the present invention, the polyolefin-polystyrene-based multi-block copolymer is characterized by satisfying the following conditions (a) to (c) as measured by gel permeation chromatography (GPC) And the following condition (d) in ¹³ C NMR (500 MHz, tetrachloroethane-d2, standard material TMS) spectrum.

(a) a weight average molecular weight of 50,000 to 300,000 g/mol,

(b) a molecular weight distribution of 1.5 to 3.0,

(c) For GPC measurement results, a Gaussian function constructed from a graph with logMw as the x-axis and dw/dlogMw as the y-axis is represented by Equation 1 below, where in Equation 1 below, each constant The numerical values satisfy -0.05<A<0.06, 4.6<B<5.5, 0.9<C<1.1, and 0.5<D<0.9, and

(d) The polyolefin block contained in the polyolefin-polystyrene-based multi-block copolymer contains one or more branch points, wherein the carbon atoms of the branch points exhibit a ratio of 36 to 40 ppm. peak, while the terminal carbon atoms of the branched chain branched from this branch point exhibited a peak of 13 to 15 ppm.

[Equation 1]

(In Equation 1 above, Mw represents the weight average molecular weight of the polyolefin-polystyrene multiblock copolymer.)

The polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention is prepared by using a specific transition metal compound with a novel structure described below as a catalyst, and has Satisfies the weight average molecular weight of Equation 1, which is an important factor in determining the physical properties of the copolymer, and thus has the ability to achieve excellent tensile properties (such as tensile strength, elongation, The weight-average molecular weight of the modulus (modulus, etc.) and the molecular weight distribution value of a specific distribution.

Regarding the condition (a), the polyolefin-polystyrene-based multi-block copolymer may have a weight average molecular weight of 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.

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

The weight average molecular weight and the number average molecular weight are the polystyrene conversion molecular weight analyzed by gel permeation chromatography (GPC), and the molecular weight distribution is determined by (weight average molecular weight)/(number average molecular weight) Ratio calculation.

As described later, Equation 1 of the 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 molecular weight distribution of the copolymer. The polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention satisfies the numerical ranges from A to D, and simultaneously satisfies the weight average molecular weight and molecular weight of the conditions (a) and (b). distribution value.

Regarding the condition (c), the following Equation 1 is derived from a Gaussian function constructed from a graph with logMw as the x-axis and dw/dlogMw as the y-axis for GPC measurements, each of the equations contained in Equation 1 The constant values satisfy −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 may be greater than -0.05, greater than -0.04, less than 0.060, or less than 0.040, the B constant may be greater than 4.6, less than 5.5, or less than 5.2, and the C constant may 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.

The above equation 1 represents the differential molecular weight distribution curve, wherein the horizontal axis is "(log(Mw))", which is measured by gel permeation chromatography (using polystyrene as a conversion standard ( The logarithmic value of the weight-average molecular weight (Mw) obtained by conversion standard)) (as described above), and the vertical axis is "dw/dlog(Mw)", which is obtained by calculating the weight-average molecular weight The value obtained by differentiating the concentration fraction (w) logarithmically (log(Mw)), which can be regarded as representing the weight fraction (in terms of the weight average molecular weight) of the polymer having the corresponding molecular weight logarithm value).

That is, in the present invention, the Gaussian function constructed from the graph in which the x-axis is logMw and the y-axis is dw/dlogMw is represented by the following equation 1, and when the values of the constants A to D are calculated, it is newly found that each of them falls in specific range.

In Equation 1 above, the A to D constants are constants representing a curve represented by a Gaussian distribution, and the height of the display distribution curve, the width of a maximum peak half value, and the maximum The central position indicated by a peak (center position indicated by a maximum peak), etc. More specifically, the A constant included in the Gaussian distribution represents the y-intercept, and the C constant represents the arithmetic mean 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 molecular weight distribution.

Regarding the condition (d), the polyolefin block contained in the polyolefin-polystyrene-based multi-block copolymer contains one or more branch points, wherein the carbon atoms of the branch points exhibit 36 to A peak of 40 ppm, while the terminal carbon atoms of the branch chain branched from this branch point exhibited a peak of 13 to 15 ppm.

Specifically, the carbon atoms of the branch point may exhibit peaks of 36.0 ppm or higher, 37.0 ppm or higher, or 37.5 ppm or higher, or may be 40.0 ppm or lower, 39.0 ppm or lower, or 38.5 ppm ppm or lower. Furthermore, the terminal carbon atoms of the branched chain branched from the branch point may exhibit a peak of 13.0 ppm or more, or 13.5 ppm or more, or may be 15.0 ppm or less, or 14.5 ppm or less.

As described above, the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention has a long branched chain in the polyolefin block, which can be branched from the branch point. Distinctive peak region identification in ^13C NMR of terminal carbon atoms of branched chains. Through 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 to typical copolymers.

The polyolefin-polystyrene-based multiblock copolymer may be one or more selected from the group consisting of: polystyrene-poly(ethylene-co-propylene)-polystyrene blocks 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.

In addition, the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention satisfies the conditions (a) to (d), and thus, can have the following tensile properties.

Specifically, the polyolefin-polystyrene-based multi-block copolymer may have a tensile strength of 10 to 100 MPa, particularly 10 to 50 MPa, more particularly 20 to 40 MPa, wherein , Tensile strength represents the maximum tensile stress at tensile and fracture (uniform load applied to the cross-sectional area).

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 Tension results in increased length as a percentage of original length when deformed in the direction of tension.

Polyolefin-polystyrene-based multi-block copolymers have a 300% modulus of 2.1 to 10.0 MPa, where the 300% modulus is defined as the amount per unit area that yields 300% elongation. Average force (as tensile stress) is expressed.

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

As described above, the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention satisfies the tensile strength, elongation at break, and 300% modulus in the above-mentioned ranges, and exhibits phase Excellent physical properties compared to typical copolymers. Furthermore, by adjusting the length and content of the polyolefin blocks using the manufacturing method provided by the present invention, copolymers that achieve specific properties according to the intended use can be prepared.

In addition, the polyolefin block of the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention may contain one or more repeating units represented by the following formula a.

[Formula a]

In the above formula a,

R ₁ can be hydrogen, alkyl having 1 to 20 carbon atoms, silyl substituted alkyl having 1 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, or Silyl-substituted arylalkyl groups of 7 to 20 carbon atoms, and

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

Alternatively, according to one embodiment of the present invention, R ₁ can be hydrogen, or an alkyl group having 3 to 20 carbon atoms.

Alternatively, according to one embodiment of the present invention, R ₁ may be hydrogen, or an alkyl group having 3 to 12 carbon atoms. Specifically, R ₁ can be hydrogen, or an alkyl group having 4 to 12 carbon atoms.

Alternatively, n may be an integer from 10 to 10,000. Specifically, n may be an integer from 500 to 7,000.

In addition, in the formula shown in the specification of the present invention, "*" represents the terminal site of the repeating unit and represents the connection site.

When the polyolefin block contains two or more repeating units represented by the above formula a, the polyolefin block may contain repeating units represented by the following formula b.

[Formula b]

In the above formula b,

R ₁ ′ and R ₁ ″ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a silyl-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 7 to 20 carbon atoms Alkyl, or silyl-substituted arylalkyl having 7 to 20 carbon atoms, wherein R1 _' and R1" are different from each other,

0 < p < 1, and

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

Or, according to an embodiment of the present invention, R1 _' and R1" can each independently be hydrogen, or an alkyl group having 3 to 20 carbon atoms, specifically, can each independently be hydrogen, or have 3 The alkyl groups of up to 12 carbon atoms, more specifically, may each independently be hydrogen, or an alkyl group having 4 to 12 carbon atoms.

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

According to an embodiment of the present invention, in the above formula b, either one of R ₁ ′ or R ₁ ″ can be hydrogen, and the other can be a non-hydrogen substituent among the above substituents.

That is, when the polyolefin block contains two or more repeating units represented by the above formula a, the structure in which R ₁ is hydrogen and the structure in which R ₁ is a non-hydrogen alkyl group having 1 to 20 carbon atoms, a silyl group The structure of a substituted alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a silyl group substituted arylalkyl group having 7 to 20 carbon atoms may be randomly attached. Specifically, structures in which R ₁ is hydrogen and structures in which R ₁ is non-hydrogen alkyl groups having 3 to 20 carbon atoms can be randomly attached.

Alternatively, more specifically, the polyolefin blocks may have a structure in which R ₁ is hydrogen and a structure in which R ₁ is an alkyl group having 3 to 12 carbon atoms randomly attached to each other. Still more specifically, the polyolefin blocks may have a structure in which R ₁ is hydrogen and a structure in which R ₁ is an alkyl group having 4 to 12 carbon atoms randomly attached to each other.

When the polyolefin block contains two or more repeating units represented by the above formula a, the polyolefin block may be in a weight ratio of 30:90 to 70:10, particularly 40:60 to 60:40, and more. In particular, the weight ratio of 45:75 to 55:25 includes a structure in which R ₁ in the above formula a is hydrogen and a structure in which R ₁ has a substituent other than hydrogen.

When the polyolefin block includes a structure in which R ₁ in the above formula a is hydrogen and a structure in which R ₁ has a substituent other than hydrogen within the above range, the prepared block copolymer contains an appropriate degree of branching within the structure (branch), thus, having a high 300% modulus value and a high elongation at break value, thereby exhibiting excellent elastic properties, and also exhibiting high molecular weight and broad molecular weight distribution, and thus, may have excellent processability.

In addition, the first polystyrene block of the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention may contain one or more repeating units represented by the following formula c .

[Formula c]

In the above formula c,

R ₂ is an aryl group having 6 to 20 carbon atoms, or a halogen-substituted aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a ring having 3 to 12 carbon atoms an alkyl group, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and

l is an integer from 10 to 1,000.

R ₂ can be phenyl, or halogen-substituted or unsubstituted phenyl, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, phenyl having 1 to 8 carbon atoms Alkoxy, or aryl having 6 to 12 carbon atoms. Alternatively, _R2 can be phenyl.

l is an integer of 10 to 1,000, specifically, an integer of 50 to 700. l In the above range, the viscosity of the polyolefin-polystyrene block copolymer produced by the production method of the present invention can be at an appropriate level.

In particular, in the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention, the polyolefin block containing the repeating unit represented by the above formula a and the polyolefin block containing the above formula c The first polystyrene blocks of the repeating units represented may be bonded to each other to form a complex block represented by the following formula d.

[Formula d]

In the above formula d,

R ₁ can be hydrogen, alkyl having 1 to 20 carbon atoms, alkyl substituted with silyl having 1 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, or silyl substituted substituted arylalkyl having 7 to 20 carbon atoms, and

R ₂ is an aryl group having 6 to 20 carbon atoms, or a halogen-substituted aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a ring having 3 to 12 carbon atoms alkyl, alkoxy having 1 to 8 carbon atoms, or aryl having 6 to 12 carbon atoms,

l is an integer from 10 to 1,000, and

n is an integer from 1 to 10,000.

Alternatively, in formula d above, R ₁ , R ₂ , 1 and n are as defined in formula a and formula c, respectively.

Alternatively, when the polyolefin block comprises the repeating unit represented by the above formula a, the complex block formed by coupling the first polystyrene block comprising the repeating unit represented by the above formula c can be represented by the following formula e.

[Formula e]

In the above formula e, R ₁ ′, R ₁ ″, R ₂ , p, l and n′ are as defined in formula a or c, respectively.

In addition, in one embodiment of the present invention, when preparing a polyolefin-polystyrene-based multi-block copolymer, a styrene-based monomer can form a polyolefin block, and a styrene-based monomer can form a polyolefin block. Monomers can be simultaneously coupled to organozinc compounds and polymerized to form individual styrene-based polymer blocks. In this disclosure, the independent styrene-based polymer block is referred to as the second polystyrene block. The second polystyrene block may include repeating units represented by the following formula f.

[Formula f]

In the above formula f,

R ₃ is an aryl group having 6 to 20 carbon atoms, or a halogen-substituted aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a ring having 3 to 12 carbon atoms an alkyl group, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and

m is an integer from 10 to 1,000.

Alternatively, according to one embodiment of the present invention, R ₃ can be phenyl, or halogen-substituted or unsubstituted phenyl, alkyl having 1 to 8 carbon atoms, ring having 3 to 12 carbon atoms An alkyl group, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Alternatively, _R3 can be phenyl.

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

That is, the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention may include the first polystyrene block including the repeating unit represented by the above formula c, and the above formula The second polystyrene block represented by f.

Accordingly, the block copolymer composition may comprise a triblock copolymer comprising a polyolefin block comprising one or more repeating units represented by the following formula a, comprising a repeating unit represented by the following formula c and a second polystyrene block comprising repeating units represented by the following formula f.

[Formula a]

[Formula c]

[Formula f]

In the above formula,

R ₁ is hydrogen, alkyl having 1 to 20 carbon atoms, silyl substituted alkyl having 1 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, or silyl substituted an arylalkyl group having 7 to 20 carbon atoms,

R ₂ and R ₃ are each independently an aryl group having 6 to 20 carbon atoms, or a halogen-substituted aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an aryl group having 3 to 20 carbon atoms A cycloalkyl group of 12 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an aryl group of 6 to 12 carbon atoms,

n is an integer from 10 to 10,000, and

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

Alternatively, in the above formula, R ₁ , R ₂ , R ₃ , n, 1, and m are as defined in formulas a, c, and f, respectively.

Preparation method of multi-block copolymer based on polyolefin-polystyrene

The method for producing a polyolefin-polystyrene-based multi-block copolymer is characterized by comprising (S1) by using an organozinc compound as a chain in the presence of a catalyst composition comprising a transition metal compound represented by the following formula 1 The transfer agent polymerizes an olefin-based monomer to form a polyolefin block, and (S2) by adding a silicon atom-containing alkyl lithium compound and a triamine compound ) in the presence of a polyolefin block and an anionic polymerization of a styrene-based monomer to form a polystyrene block.

The method for preparing the polyolefin-polystyrene-based multi-block copolymer can be achieved by using a transition metal compound represented by formula 1, which is efficiently used for the polymerization of olefin-based monomers, as a catalyst. media to form polyolefin chains, followed by continuous anionic polymerization of styrene to form polyolefin-polystyrene blocks as described hereinafter, to form tan delta peaks exhibiting specific heights of tan delta peaks and half widths of tan delta peaks Multi-block copolymer based on polyolefin-polystyrene.

Step (S1)

Step (S1) is to polymerize an olefin-based monomer by using an organozinc compound as a chain transfer agent in the presence of a catalyst composition comprising a transition metal compound represented by the following formula 1 to form The step of polyolefin block.

[Formula 1]

In the above 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, an alkyl group having 3 to 20 carbon atoms Cycloalkyl of atoms, aryl group of 6 to 20 carbon atoms, arylalkoxy of 7 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, 7 to 20 carbon atoms an alkylaryl group, an alkylsilyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

Two or more of R ₁ to R ₁₁ adjacent to each other 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

X ₁ and X ₂ are each independently hydrogen, halogen, hydroxyl, amine group, thio group, silicon group, cyano group, nitro group, alkyl group having 1 to 20 carbon atoms, having 2 to 20 carbon atoms Alkenyl group of carbon atoms, alkynyl group of 2 to 20 carbon atoms, cycloalkyl group of 3 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, alkyl group of 7 to 20 carbon atoms Aryl, arylalkyl groups having 7 to 20 carbon atoms, heteroaryl groups having 5 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, 6 to 20 carbon atoms Aryloxy group of atoms, alkylamino group with 1 to 20 carbon atoms, arylamino group with 6 to 20 carbon atoms, arylamino group with 1 to 20 carbon atoms alkylthio group of atoms, arylthio group with 6 to 20 carbon atoms, alkylsilyl group with 1 to 20 carbon atoms, or aryl group with 6 to 20 carbon atoms Silicon based.

When the polymerization reaction is carried out in the presence of an excess of chain transfer agent (eg (Et) ₂ Zn) relative to the catalyst, the olefin polymer chain causes rapid transalkylation between zinc (Zn) and hafnium (Hf). ) to uniformly grow from dialkylzinc to achieve living polymerization, which is called coordinated chain transfer polymerization (CCTP). Commonly used metallocene catalysts cannot accept living polymerization through β-elimination procedures, and a few known catalysts suitable for CCTP only allow single polymerization of ethylene and alpha-olefin. (single polymerization), so it is extremely difficult to carry out the polymerization of ethylene and α-olefin through CCTP. Therefore, it is extremely difficult to carry out living polymerization via CCTP and prepare block copolymers using common transition metal compounds as catalysts.

On the other hand, the hafnium compound represented by the above formula 1 is a [N ^amido , N,C ^aryl ]HfMe ₂ -type composite ([N ^amido , N,C aryl] ^HfMe ₂ -type composite), which includes 1, 2,3,4-tetrahydro-1,10-phenanthroline skeleton (1,2,3,4-tetrahydro-1,10-phenanthroline skeleton) and Hf-C(aryl) bond (Hf-C(aryl) bond), which exhibits excellent alpha-olefin incorporation capacity in the polymerization of ethylene and alpha-olefins. In particular, the molecular weight of the olefin polymer or the content of α-olefin varies depending on the content of the chain transfer agent, which indicates that the compound is successfully used for CCTP and that the β-removal reaction is infrequent and negligible. That is, using the hafnium compound represented by the above formula 1, the polymerization of ethylene and the α-olefin-based monomer can be carried out by living polymerization through CCTP, and block copolymers having various block compositions can be successfully prepared.

In addition, CCTP using a hafnium compound can be converted and subjected to an anionic styrene polymerization reaction to synthesize a polyolefin-polystyrene block copolymer. As mentioned above, the hafnium compound can be used as a catalyst for the preparation of olefin polymers, which is a unique feature that can be achieved by the novel structure of the hafnium compound represented by the above formula 1.

Specifically, in Formula 1 above, R ₁ to R ₁₁ may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a cycloalkyl group having 6 to 20 carbon atoms. an aryl group of carbon atoms. Preferably, R ₁ to R ₁₀ may be hydrogen, and meanwhile, R ₁₁ may be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. More preferably, R ₁ to R ₁₀ may be hydrogen, and at the same time, R ₁₁ may be hydrogen, or an alkyl group having 1 to 20 carbon atoms.

Alternatively, in Formula 1 above, R ₁ to R ₁₁ may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. At this time, 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 may be connected to each other to form a benzene ring, and at the same time, R ₁₁ may be an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

Alternatively, in the above formula 1, R ₁ , R ₂ , and R ₅ to R ₁₀ may be hydrogen, and R ₃ , R ₄ , and R ₁₁ may each independently be hydrogen, or an alkane having 1 to 20 carbon atoms group, wherein R ₃ and R ₄ can be attached to each other to form an aromatic ring having 5 to 20 carbon atoms, such as a benzene ring.

And, X ₁ and X ₂ 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, each independently may be an alkyl group having 1 to 20 carbon atoms, wherein X ₁ and X ₂ may be the same as each other.

In the present invention, the term "alkyl" means a straight or branched chain hydrocarbon moiety.

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

In the present invention, "aryl" preferably has 6 to 20 carbon atoms, specifically phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, Anisolyl, etc., but not limited thereto.

In the present invention, "alkylaryl" means an aryl group substituted with the above-mentioned alkyl group.

In the present invention, "arylalkyl" means an alkyl group substituted with the above-mentioned aryl group.

In this specification, "alkylsilyl" may be a silicon group substituted with an alkyl group having 1 to 20 carbon atoms, such as trimethylsilyl or triethylsilyl.

In the present invention, "alkylamino" refers to an amino group substituted with the above-mentioned alkyl group, such as dimethylamino group, diethylamino group, etc., but not limited to this.

In the present invention, unless stated otherwise, "hydrocarbyl" 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, alkylaryl, or arylalkyl, regardless of structure.

More specifically, the hafnium compound represented by the above formula 1 may be a hafnium compound represented by the following formula 1a or 1b.

[Formula 1a]

[Formula 1b]

In the above formulas 1a and 1b,

R ₁₁ is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, arylalkoxy groups having 7 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkylaryl groups 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, and

X ₁ and X ₂ are each independently hydrogen, halogen, hydroxyl, amine, thio, silyl, cyano, nitro, alkyl having 1 to 20 carbon atoms, alkene having 2 to 20 carbon atoms radicals, alkynyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkylaryl groups having 7 to 20 carbon atoms, Arylalkyl groups of 7 to 20 carbon atoms, heteroaryl groups of 5 to 20 carbon atoms, alkoxy groups of 1 to 20 carbon atoms, aryloxy groups of 6 to 20 carbon atoms, 1 Alkylamino groups with to 20 carbon atoms, arylamine groups with 6 to 20 carbon atoms, alkylthio groups with 1 to 20 carbon atoms, arylthio groups with 6 to 20 carbon atoms, 1 to 20 carbon atoms Alkylsilyl groups of to 20 carbon atoms, or arylsilyl groups of 6 to 20 carbon atoms.

The hafnium compound may be represented by any one of Formula 1-1 to Formula 1-5, but is not limited thereto. Any hafnium compound corresponding to Formula 1 is 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 can be prepared by including a step of reacting a compound represented by the following formula 2 with a compound represented by the following formula 3.

[Formula 2]

[Formula 3]

In the above formula,

The definitions of R ₁ to R ₁₁ , and X ₁ and X ₂ are as described above.

In addition, when preparing the hafnium compound represented by the above formula 1, depending on the structure of the finally prepared hafnium compound, the steps of preparing a ligand compound may be performed differently as follows.

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

[Reaction 1]

Alternatively, as shown in the following reaction formula 2, when R ₃ and R ₄ do not form a ring with each other and R ₁₁ is a substituent that is not a hydrogen atom in the structure of the ligand compound, an organolithium compound (rganolithium compound) is used to first introduce R ₁₁ It is then hydrogenated under a ruthenium catalyst to prepare a ligand compound.

[Reaction 2]

Alternatively, as shown below, when R ₃ and R ₄ are connected to each other and form an aromatic ring having 5 to 20 carbon atoms and R ₁₁ is a substituent other than a hydrogen atom in the structure of the ligand compound, an organolithium compound can be used R ₁₁ is introduced first, and then, in order to prevent hydrogenation of aromatic rings such as naphthyl, hydrogenation is carried out under a Pd/C catalyst to prepare a ligand compound.

[Reaction 3]

That is, hafnium compounds can be prepared by alkylation and hydrogenation of compounds that are precursors of ligand compounds under suitable reagents and reaction conditions to prepare ligand compounds, and then introducing hafnium therein. The specific type of alkylation reagent, reaction temperature and pressure can be appropriately changed by those skilled in the art considering the structure of the final compound and experimental conditions.

In the present invention, the organozinc compound is a material used as a chain transfer agent that initiates chain transfer during preparation in a polymerization reaction to enable preparation of a copolymer, and specifically may be a compound represented by the following formula 4.

[Formula 4]

In the above formula 4,

A is an alkylene having 1 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, or an arylene substituted with halogen having 6 to 20 carbon atoms, having an alkyl group of 1 to 12 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, and

B is an aryl group having 6 to 12 carbon atoms substituted with an alkenyl group having 2 to 12 carbon atoms.

Alternatively, A may be an alkylene group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen substituted aryl group having 6 to 20 carbon atoms, 1 to 12 carbon atoms an alkyl group of 1 to 12 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, and

B may be an aryl group having 6 to 12 carbon atoms substituted with an alkenyl group 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 an alkenyl-substituted aryl group, the aryl group is attached to A and the double bond of the alkenyl group substituted in the aryl group can be located in the outermost portion of Formula 4.

When the organozinc compound reacts with one or more olefin-based monomers in the presence of the catalyst composition, the olefin-based monomer can be inserted between the zinc (Zn) of the organo-zinc compound and the organic group (A). to achieve aggregation.

The organozinc compound may be in an amount of 1 to 200 equivalents (based on 1 equivalent of the transition metal compound of formula 1 above), especially in an amount of 10 to 100 equivalents (based on 1 equivalent of the transition metal of formula 1 above) compound as a reference) and mixed.

The organozinc compound does not contain impurities such as THF and a large amount of magnesium salts, and thus, can be supplied in high purity, and thus, can be used as a chain transfer agent, as well as facilitate the polymerization of olefins.

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 Formula 1, and one known in the art can be used as the co-catalyst. For example, one or more selected from the following formulae 5 to 7 may be used as a cocatalyst.

[Formula 5]

[Formula 6]

[Formula 7]

In the above formula,

R _a is each independently a halogen radical, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms,

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 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

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

The compound represented by the above formula 5 is not particularly limited as long as it is an alkylaluminoxane. Preferred examples thereof include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc. A particularly preferred compound is methylaluminum oxane.

The compound represented by the above formula 6 is not particularly limited, but preferable examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride (dimethylchloroaluminum), triisopropylaluminum, tri-s-butylaluminum (tri-s-butylaluminum), tricyclopentylaluminum, triamylaluminum, triisoamylaluminum, trihexylaluminum, trioctylaluminum , ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide (dimethylaluminum ethoxide), trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc. Particularly preferred compounds are selected from the group consisting of trimethylaluminum, triethylaluminum, and triisobutylaluminum.

Examples of the compound represented by the above 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, tetra[3,5-bis(trifluoromethyl) ) phenyl] borate dioctadecylmethylammonium Ammonium (triethylammonium tetraphenylborate), tributylammonium tetraphenylborate (tributylammonium tetraphenylborate), trimethylammonium tetraphenylborate (trimethylammonium tetraphenylborate), tripropylammonium tetraphenylborate (tripropylammonium tetraphenylborate), tetrakis (p-toluene) base) trimethylammonium borate (trimethylammonium tetra(p-tolyl) borate), tetrakis (o, p-dimethylphenyl) borate trimethylammonium (trimethylammonium tetra(o, p-dimethylphenyl) borate), tetra ( tributylammonium tetra(p-trifluoromethylphenyl) borate, trimethylammonium tetra(p-trifluoromethylphenyl) borate ), tributylammonium tetrapentafluorophenylborate, N,N-diethylanilinium tetrapentylborate (N,N-diethylanilidium tetrapetylborate), N,N-diethylanilinium tetraphenylborate N,N-diethylanilidium tetraphenylborate, N,N-diethylanilinium tetrakis (pentafluorophenyl) borate (N,N-d iethylanilidium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, tetraphenyl trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl) borate, tetra(p-tolyl) borate tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate, tetrakis(o,p-dimethylphenyl)borate (o, p-dimethylphenyl) borate trimethylammonium (trimethylammonium tetra(o, p-dimethylphenyl) borate), tetra (p-trifluoromethylphenyl) borate tributylammonium (tributylammonium tetra (p -trifluoromethylphenyl)borate), trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilinium tetraphenylborate (N,N-diethylanilinium tetraphenylborate), N,N-diethylanilinium tetrakis(pentafluorophenyl)borate diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, tetrakis(p-trifluoromethyl) triphenylcarbonium tetra(p-trifluoromethylphenyl) borate, triphenylcarbonium tetrapentafluorophenylborate, or combinations thereof; and 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(p-tolyl)aluminum triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum trifluoromethylphenyl) aluminum), trimethylammonium tetra(p-trifluoromethylphenyl) aluminum), tributylammonium tetra (pentafluorophenyl) aluminum (tributylammonium tetrapentafluorophenylaluminum), N ,N-diethylanilinium tetraphenylaluminum (N,N-diethylanilinium tetraphenylaluminum), N,N-diethylanilinium tetraphenylaluminum (N,N-diethylanilinium tetraphenylaluminum), N,N-diethyl N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium, tetrapentatentraphenylaluminum, triphenylphos phonium tetraphenylaluminum), trimethylphosphonium tetraphenylaluminum, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, or combinations thereof, but not limited to this.

In particular, the cocatalyst used in the present invention can be the compound represented by the above formula 7, specifically, dioctadecylmethylammonium tetrakis (pentafluorophenyl)borate.

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

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

In addition, the hafnium compound represented by Formula 1 and the cocatalyst can also be used in the form of being supported on a carrier. The carrier may be silica or alumina, but is not limited thereto.

The olefin monomer introduced as the reaction material in step (S1) can be ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, Monomers formed from 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene, or their mixtures, etc. . The olefin monomers may be used alone or in combination of two or more.

Step (S1) can be performed, for example, in a homogeneous solution state. At this time, as the solvent, a hydrocarbon solvent or an olefin monomer itself can be used as a medium. The hydrocarbon solvent may be an aliphatic hydrocarbon solvent having 4 to 20 carbon atoms, specifically isobutane, hexane, cyclohexane, methylcyclohexane, and the like. The solvent may be used alone or in combination of two or more.

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

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

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

Step (S2)

Step (S2) is carried out following step (S1) and forms polyphenylene by anionic polymerization of a polyolefin block and a styrene-based monomer in the presence of a silicon atom-containing alkyllithium compound and a triamine compound The step of preparing polyolefin-polystyrene-based multi-block copolymer by ethylene block.

_In the step (S2), the styrene _- based monomer can be continuously inserted into the zinc- Between the zinc-carbon bonds, and at the same time, the styrene group present at the end of the compound formed by step (S1) can participate as a styrene-based group to be attached to the polystyrene chain The copolymerization site of the monomers. In addition, the multi-block copolymers prepared by the above procedure can be easily quenched by the reaction of an end group using water, oxygen or organic acids, by which the multi-block copolymers are transformed Industrially available multi-block copolymers based on polyolefin-polystyrene.

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 aryl group having 6 to 20 carbon atoms, ethylene substituted with a phenyl group, and the like, such as benzene. Ethylene (styrene).

The alkyllithium compound containing a silicon atom may be a compound represented by the following formula 8.

[Formula 8]

Alkyllithium compounds containing silicon atoms are materials widely used as initiators for anionic polymerization, and are easily used in the present invention.

The triamine compound may be a compound represented by Formula 9 below.

[Formula 9]

Triamine compounds are compounds used to improve the reactivity of alkyllithium compounds as bases or as nucleophiles (by coordinating well with lithium), and are readily available and inexpensive .

The present invention newly uses the compounds of formula 8 and 9 (eg Me ₃ SiCH ₂ Li·(PMDETA)) as the initiator of step (S2), thus, it can inhibit polystyrene homopolymer, polyolefin homopolymer, and the production of polyolefin-polystyrene diblock copolymers, and maximizing the production of polyolefin-polystyrene-based multi-block copolymers, which is the goal of the present invention.

The alkyllithium compound containing a silicon atom and represented by Formula 8 and the triamine compound represented by Formula 9 may be mixed and introduced into an aliphatic hydrocarbon solvent, or the alkyllithium compound containing a silicon atom and represented by Formula 8 and represented by Formula 9 The triamine compounds can be introduced sequentially.

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

The anionic polymerization of step (S2) can be carried out in a batch, semi-continuous, or continuous manner, and can also be carried out in two or more steps with different reaction conditions.

The anionic polymerization time of the 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 all the styrene-based monomers introduced into the multi-block copolymer.

As described above, in the production method of the present invention, the polyolefin chain is grown by olefin polymerization using the above-mentioned organozinc compound represented by the above formula 4, and then anionic polymerization of styrene is continuously carried out to prepare polyolefin-polystyrene-based The multi-block copolymer, through which, can efficiently prepare a polyolefin-polystyrene-based multi-block copolymer with improved physical properties compared to the prior art, and thus can be easily used in industry.

The method of preparing a polyolefin-polystyrene based multiblock copolymer according to one embodiment of the present invention is the same as the preparation in which styrene and diene are subjected to anionic polymerization followed by a two-step hydrogenation procedure to prepare polyolefin-polyethylene The typical process for styrene-based multi-block copolymers differs and is characterized by the preparation of polyolefin-polystyrene-based multi-block copolymers without hydrogenation of the double bonds in the copolymer backbone. Therefore, the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition of the present invention is characterized in that the polyolefin-polystyrene-based multi-block copolymer does not contain untreated An unsaturated bond that is saturated and is present during the hydrogenation procedure of the double bond of the main chain.

Also, the thermoplastic resin composition according to an embodiment of the present invention having the above-mentioned composition may contain each component in an appropriate content in order to satisfy the application and correspondingly required physical properties. For example, in the present invention, the thermoplastic resin composition may comprise 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-based multi-block copolymers. The thermoplastic resin composition according to the present invention includes polypropylene and a polyolefin-polystyrene-based multi-block copolymer in the above weight ratio, and thus can exhibit improved low temperature and room temperature impact strength properties and high flow properties. When the content of the polyolefin-polystyrene-based multi-block copolymer contained in the thermoplastic resin composition is too small, the impact strength will deteriorate, and the polyolefin-polystyrene-based multi-block copolymer When the content is too large, the fluidity of the thermoplastic resin composition will deteriorate. The mixing ratio can be controlled in consideration of the importance of the physical properties of the polypropylene and the polyolefin-polystyrene-based multi-block copolymer.

The thermoplastic resin composition according to the present invention contains a polyolefin-polystyrene-based multi-block copolymer satisfying the conditions (a) to (d), and thus, even if a relatively small amount of polyolefin-polystyrene-based multi-block copolymer is contained The main multi-block copolymer also exhibits excellent low temperature and room temperature impact strength.

The thermoplastic resin composition according to an embodiment of the present invention may optionally further include inorganic fillers, polypropylene and polyolefin-polystyrene-based multi-block copolymers to improve the performance of the thermoplastic resin composition. mechanical properties.

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 powder-type filler may be a natural silicic acid or a silicate, such as fine powder talc, kaolinite, calcined clay, or sericite; carbonates, such as precipitated calcium carbonate, heavy calcium carbonate or magnesium carbonate; hydroxides such as aluminium hydroxide or magnesium hydroxide; oxides such as zinc oxide, magnesium oxide, or titanium oxide; synthetic silicic acid Or silicates, such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid or silicic anhydride, and silicon carbide, etc. . In addition, the flake-type filler may be mica or the like. The fiber filler can be basic sulfuric acid magnesium whisker, calcium titanate whisker, boric acid aluminum whisker, sepiolite, treated Mineral fiber (processed mineral fiber) (PMF), potassium titanate, etc. In addition, the hollow spherical filler may be a glass balloon or the like. Among the above, the inorganic filler may be talc.

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

Specifically, the inorganic fillers may be physically surface-treated or using surface-treating agents such as silane coupling agents, higher fatty acids, fatty acid metal salts, unsaturated organic acids, organic titanates, Chemical surface treatment of resin acid or polyethylene glycol.

Furthermore, the average particle size (D ₅₀ ) of the inorganic filler may be 1 μm to 20 μm, particularly 3 μm to 15 μm, more particularly 5 μm to 10 μm. When the average particle size of the inorganic filler is too small, when it is mixed with polypropylene and polyolefin-polystyrene-based multi-block copolymers, it is difficult to obtain uniform dispersion due to the aggregation between the inorganic filler particles. , the effect of improving the mechanical properties of the thermoplastic resin composition will be insignificant. Furthermore, when the average particle diameter of the inorganic filler is too large, there is a risk of deterioration of physical properties due to deterioration of the dispersibility of the inorganic filler itself.

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

The content of the above-mentioned inorganic fillers may be 0.1 parts by weight to 40 parts by weight based on 100 parts by weight of the thermoplastic resin composition. When the content of the inorganic filler in the thermoplastic resin composition (based on 100 parts by weight of the thermoplastic resin composition) is less than 0.1 part by weight, the improvement effect due to the inclusion of inorganic fillers will not be significant; and when it is greater than 40 parts by weight, the thermoplastic resin The workability of the resin composition deteriorates. More specifically, the content of the inorganic filler may be 0.1 wt % to 20 wt % based on the total weight of the thermoplastic resin composition.

The thermoplastic resin composition according to one embodiment of the present invention that satisfies the above composition and content conditions can be prepared by adding polypropylene and selectively inorganic fillers to polyolefin-polystyrene-based compositions. The multiblock copolymer is then heat treated. At this time, the type and content of polypropylene are as described above.

The mixing procedure can be carried out according to typical methods. Specifically, mixing can be performed using a super mixer or a ribbon mixer.

In addition, according to the needs of the mixing process, additives such as antioxidants, heat stabilizers, UV stabilizers, antistatic agents, etc. may be further included, and in order to improve paintability (paintability), optionally further used in an appropriate content range with a small amount Additives for adhesive resins or polar groups.

Additionally, the heat treatment procedure can be performed at temperatures above the melting point of polypropylene and at 210°C or lower. The heat treatment procedure can be carried out using various blending processing devices such as twin-screw extruder, single-screw extruder, roll-mill, kneader , or Banbury mixer.

The thermoplastic resin composition according to an embodiment of the present invention prepared according to the above preparation method can exhibit excellent low-temperature impact strength properties and high flow properties, and in addition, can exhibit excellent room temperature impact strength (room temperature impact strength) properties.

Specifically, the thermoplastic resin composition can satisfy the following physical properties (A) to (C).

(A) Room temperature impact strength of 3 to 100 kgf m/m

(B) Low temperature (-40°C) impact strength of 2 to 120 kgf m/m

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

(A) Room temperature impact strength, measured by the ASTM D256 method, may be 3 to 100 kgf·m/m, particularly 20 to 100 kgf·m/m, more particularly 30 to 90 kgf·m/m.

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

(C) Melt flow rate (MFR), measured according to ASTM-D 1238 at 230°C and 2.16 kg load, may be 0.5 to 200 g/10 min, especially 3 to 100 g/10 min , more particularly 7 to 50 g/10 min.

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, and household products. injection molding), materials such as automobiles, wires, toys, textiles or medical products. In particular, the thermoplastic resin composition has excellent low temperature and room temperature toughness and impact strength, and also has excellent physical properties such as heat resistance and rigidity, and thus can be used for automobile interior and exterior parts.

According to another embodiment of the present invention, there are provided molded bodies and automobile parts produced by using the thermoplastic resin composition satisfying the above-mentioned physical property requirements.

The molded body may specifically be a blow molding molded body, an inflation molded body, a cast molded body, an extrusion laminate molded body, Extrusion molded body, foam molded body, injection molded body, sheet, film, fiber, monofilament, non-woven fabric, and the like.

In addition, the automobile parts may be used for interior and exterior parts of automobiles, and the like.

Example

Hereinafter, the present invention will be described in detail with reference to Examples. However, the following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention.

< Preparation of transition metal compounds >

Preparation example 1

(i) Preparation of ligand compounds

Isopropyllithium (0.45 mL, 0.36 mmol, 0.79 M in pentane) was slowly added to 2-naphthyl-1,10-phenanthroline (2-naphthyl-1,10-phenanthroline (2) in toluene (8 mL) at -10°C). -naphthyl-1,10-phenanthroline) (0.789 g, 2.58 mmol). After stirring at room temperature for 3 hours, degassed _H2O (3 mL) was added. The aqueous layer was removed by 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 charging _H2 gas to 5 bar, the mixture was stirred at room temperature for 12 hours. _H2 gas was released and the catalyst residue was filtered over celite and removed. The solvent was removed and the residue was purified by silica gel column chromatography using ethyl acetate/hexane (1/3, v/v). Obtained as a pale yellow sticky solid (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, 126.10, 126.61, 126.86, 128.69, 129.03, 129.03, 129.03 129.28, 132.20, 134.71, 136.41, 137.64, 139.79, 141.75, 155.92 ppm.

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

(ii) Preparation of transition metal compounds

[Formula 1-3]

MeMgBr (1.24 mL, 3.11 M in diethyl ether) was added dropwise to a stirred suspension (0.300 g, 0.938 mmol) of HfCl4 in toluene ( ₈ mL) at -78 °C. After stirring for 1 hour at a temperature in the range of -40°C and -35°C, the solution was cooled again to -78°C. A solution of the ligand compound (0.366 g, 1.00 mmol) in toluene (4 mL) (0.24 g, 0.94 mmol) was added dropwise. The resulting solution was stirred at a controlled temperature ranging from -40°C to -35°C for 2 hours and then at room temperature overnight. The solvent was removed using a vacuum line and the residue was extracted with toluene (50 mL). A dark brown powder (0.226 g, 47%) was obtained by pulverization in hexane. 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, 124.55, 125.48, 126.97, 129.97, 129.97, 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 cocatalyst >

Combine excess K ⁺ [B(C ₆ F ₅ ) ₄ ] ^- (0.633 g, 0.881 mmol, assumed pure) with [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [Cl] ^- (0.404 g , 0.705 mmol) in toluene (anhydrous, 10 mL) was reacted in a glove box for 1 hour at room temperature. After filtration through celite, the solvent was removed using a vacuum line. The residue was dissolved in methylcyclohexane (4 mL) and filtered again through celite. The solvent was removed to give 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 Organozinc Compounds >

Borane dimethyl sulfide (1.6 mL, 3.2 mmol) was slowly introduced into triethylborane (0.6 g) with stirring, and then reacted for 90 minutes. The mixture was slowly introduced into divinylbenzene (3.8 g) dissolved in anhydrous diethylether cooled to -20°C, followed by stirring overnight. The solvent was removed with a vacuum pump, then diethylzinc (0.8 g) was added. The reaction was carried out at 0°C for 5 hours while the produced triethylborane was removed by distillation under reduced pressure. Excess divinylbenzene and diethylzinc were removed by distillation under reduced pressure at 40°C. Methylcyclohexane (150 mL) was added to dissolve the product again, and then the solid compound produced as a by-product was filtered and removed using celite to prepare the organozinc compound represented by the above formula.

< polyolefin - Preparation of polystyrene-based multi-block copolymers >

Implementation preparation 1

The Parr reactor (1 gallon) was vacuum dried 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.

The reactor was filled with methylcyclohexane (1,200 g) containing Oc3Al (1466.4 mg, 1,000 μmol _- Al/25 wt% in hexane) as a scavenger, and 1-hexene (560 g) g) As an olefin monomer, and the temperature was set to 90°C. A solution of the organozinc compound (3,100 μmol) in methylcyclohexane (3.85 g) was filled as a chain transfer agent, and then injected with a solution containing [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [B(C ₆ ] A methylcyclohexane solution (1.68 g) of the transition metal compound of Preparation 1 (12.0 μmol-Hf) activated by _F5 ) ₄ ] ^- (12.0 μmol) in methylcyclohexane. 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 in the range of 90 to 120°C, and the residual ethylene gas was vented.

When the temperature reached 90°C, Me3SiCH2Li prepared by mixing Me3SiCH2Li (244.8 _mg , 2.6 mmol) _PMDETA ( _{495.1 mg} , 2.86 mmol) in methylcyclohexane (3.85 g) was added • (PMDETA) solution. The temperature was maintained at 90°C for 30 minutes during stirring, then styrene (104.0 g) was injected. Use a heating mantle to adjust the temperature in the range of 90 to 100°C.

Complete conversion of styrene was confirmed ^by1H NMR analysis of an aliquot. After complete conversion of styrene, 2-ethylhexanoic acid and ethanol were injected continuously. The obtained polymer mass (300 g) was dried in a vacuum oven at 80° C. overnight to prepare a polyolefin-polystyrene-based multi-block copolymer.

Implementation 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 organozinc compound and the amount of styrene used were different, as shown in Table 1 below.

Implementation preparation 3 and 4

The polyolefin-polystyrene-based multi-block copolymers were each prepared by repeating the same method as in Preparation Example 1.

Comparative preparation example 1

G1651 from Kraton Company was used as a commercially available SEBS.

Comparative preparation example 2

Using a compound represented by the following formula as a transition metal compound, a polyolefin-polystyrene-based multi-block copolymer was prepared by the following method.

[Comparison 1]

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

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 solution obtained by stirring the transition metal compound and (C ₁₈ H ₃₇ )N(Me)H ⁺ [B(C ₆ F ₅ ) ₄ ] ^- (4.0 μmol) in benzene for 2 hours was obtained by mixing the three A solution (1.0 g) obtained by dissolving octylaluminum (50 μmol, 18.3 mg) in methylcyclohexane (15 g) was diluted. Immediately after the catalyst solution was injected into the high pressure reactor, ethylene-propylene mixed gas was injected therein at a pressure of 20 bar (10 bar for propylene). The temperature is adjusted in the range of 95 to 115°C. Due to monomer consumption, the pressure was gradually reduced and the polymerization procedure was carried out at 45°C for 60 minutes, after which the remaining gas was vented.

Me3SiCH2Li (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 at 90°C to 100°C. Styrene (7.8 g) was injected into the high pressure reactor and then reacted for 5 hours while the temperature was maintained at 90°C to 100°C for complete conversion of styrene monomer. After complete conversion of the styrene monomer, acetic acid and ethanol were continuously injected. The polymer was obtained and then dried in a vacuum oven at 180°C overnight.

Experimental example 1

For the polyolefin-polystyrene-based multi-block copolymers of Example Preparations 1 to 3 and Comparative Preparation 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 the following table 2.

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

The measurements are carried out by means of nuclear magnetic resonance (NMR). Using a Bruker 600MHz AVANCE III HD NMR apparatus, ^1H NMR was measured under conditions of ns=16, d1=3s, solvent=TCE-d2, and 373K, then the TCE-d2 solvent peak was calibrated to 6.0 ppm. The _CH3 of 1-propene was confirmed to be at 1 ppm and the _{CH3 -} related peak (triplet) by the butyl branch of 1-hexene was confirmed to be close to 0.96 ppm to calculate the content. In addition, the styrene content was calculated using an aromatic peak near 6.5 to 7.5 ppm.

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

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

- String: PL Olexis

- Solvent: TCB (trichlorobenzene)

- Flow rate: 1.0 ml/min

- Sample concentration: 1.0 mg/ml

- Injection amount: 200 μl

- Column temperature: 160 ℃

- Detector: Agilent High Temperature RI detector

- Standard: Polystyrene

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

(3) Calculation of constants A to D in Equation 1

To calculate the values of the constants A to D, Origin's Nonlinear Curve Fit was used to fit the GPC measurements with a Gaussian function.

In addition, FIG. 3 shows a graph showing the polyolefin-polystyrene-based multi-block copolymer obtained in Preparation Example 1 by means of Equation 1.

Experimental example 2

For the polyolefin-polystyrene-based multi-block copolymers of Preparation Examples 1 to 3 and Comparative Preparation Example 1, the carbon atoms at the branch point and the terminal carbon atoms of the branch chain branched from the branch point The peak values are summarized and described in Table 3 below.

Specifically, a Bruker AVANCEIII 500 MHz NMR was used as the device, and about 50 mg of the sample was added to 1.2 ml of TCE-d2 (tetrachloroethane-d2) as a solvent, and in a heating block at Heating at 100°C for 1 hour with vortexting 2 to 3 times. The sample was confirmed to be homogeneously melted, and then moved to an MNR tube to measure the ¹³ C NMR spectrum at 100°C.

Experimental example 3

(1) Tensile properties

Each test piece was prepared according to the ASTM D412 tensile test method, and its tensile strength, elongation, and 300% modulus were measured.

As shown in Table 4, it was confirmed that the block copolymer of Preparative Example 1 exhibited tensile strength, elongation, and tensile strength of 300% modulus compared to the copolymer of Comparative Preparative Example 1 which did not satisfy all of the above conditions The properties are all excellent properties at a predetermined level.

Example 1 - Preparation of thermoplastic resin composition

To 50 parts by weight of the polyolefin-polystyrene-based multi-block copolymer prepared in Preparation Example 1, 50 parts by weight of a melt index (230° C., 2.16 kg) with a melt index of 30 was added. Highly crystalline impact copolymer polypropylene (CB5230, product of Korea Petrochemical Ind. Co., LTD) of g/10 min, and solution blending in xylene using a reactor to prepare Thermoplastic resin composition compound. At this time, the temperature was 200°C to 230°C, the rotation speed of the impeller was 400 rpm, and the blending time was 4 hours. After blending was complete, the compound was withdrawn and dried in a vacuum oven at 100°C overnight.

Example 2 to 4 - Preparation of thermoplastic resin composition

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 that in Example 1. The prepared polyolefin-polystyrene-based multi-block copolymer.

Comparative example 1 and 2 - Preparation of thermoplastic resin composition

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 Comparative Preparation Examples 1 and 2 was used in place of that in Example Preparation 1. The prepared polyolefin-polystyrene-based multi-block copolymer.

Experimental example 4

1) Low temperature impact strength

Low temperature impact strength is measured after aging by subjecting the subject to low temperature (-40°C) for 6 hours or more, performed according to ASTM D256.

2) Melt Flow Rate (MFR)

Measurements were carried out according to ASTM-D 1238 at 230°C and a load of 2.16 kg.

As can be seen from Table 5 above, it was confirmed that the thermoplastic resin compositions of Examples 1 to 4 respectively comprising the polyolefin-polystyrene-based multi-block copolymers of Preparation Examples 1 to 4 had excellent low temperature impact strength and The melt flow rate, therefore, has significantly superior overall physical properties compared to the thermoplastic resin compositions of Comparative Examples 1 and 2.

Fig. 1 shows a ligand compound used in the preparation of a polyolefin-polystyrene-based multi-block copolymer contained in a thermoplastic resin composition according to an embodiment of the present invention ) of ¹ H NMR and ¹³ C NMR spectra;

Fig. 2 shows a transition metal compound used in the preparation of a polyolefin-polystyrene-based multi-block copolymer contained in a thermoplastic resin composition according to an embodiment of the present invention ) of ¹ H NMR and ¹³ C NMR spectra; and

[ Fig. 3] Fig. 3 is a diagram showing a polyolefin-polystyrene-based multi-block copolymer contained in a thermoplastic resin composition according to an embodiment of the present invention by Equation 1. [Fig.

Claims (9)

A thermoplastic resin composition comprising: (1) polypropylene; and (2) a polyolefin-polystyrene-based multi-block copolymer that satisfies the following measured by gel permeation chromatography (GPC) Conditions (a) to (c) and the following conditions (d) ^in13C NMR (500 MHz, tetrachloroethane-d2, standard material TMS) spectrum: (a) a weight average molecular weight of 50,000 to 300,000 g/mol, (b) The molecular weight distribution is 1.5 to 3.0, (c) For GPC measurements, the Gaussian function constructed from the graph with logMw as the x-axis and dw/dlogMw as the y-axis is given by the following Equation 1 represents where, in the following Equation 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 (d) the polyolefin - the polyolefin block contained in the polystyrene-based multi-block copolymer contains one or more branching points, wherein the carbon atoms of the branching points exhibit 36 to 40 ppm peak, while the terminal carbon atoms of the branch chain branched from this branch point exhibit a peak of 13 to 15 ppm, [Equation 1]

Wherein, in the above equation 1, Mw represents the weight average molecular weight of the polyolefin-polystyrene-based multi-block copolymer. The thermoplastic resin composition of claim 1, wherein the constant values of the above equation 1 satisfy -0.04<A<0.040, 4.6<B<5.2, 0.91<C<1.09, and 0.6<D<0.9. The thermoplastic resin composition of claim 1, wherein the weight average molecular weight is 60,000 g/mol to 250,000 g/mol. The thermoplastic resin composition of claim 1, wherein the molecular weight distribution is 1.6 to 2.3. The thermoplastic resin composition of claim 1, wherein the polyolefin-polystyrene-based 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-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 Copolymers, polystyrene-poly(ethylene-co-1-heptene)-polystyrene block copolymers, and polystyrene-poly(ethylene-co-1-octene)-polystyrene block copolymers thing. The thermoplastic resin composition of claim 1, wherein the polyolefin-polystyrene-based multi-block copolymer comprises a polystyrene-based block in an amount of 10 wt% to 30 wt%. The thermoplastic resin composition of claim 1, wherein the polyolefin-polystyrene-based multi-block copolymer is prepared without hydrogenation of double bonds in the main chain of the copolymer. The thermoplastic resin composition of claim 1, wherein the weight ratio of the (1) polypropylene and the (2) polyolefin-polystyrene-based multi-block copolymer is 10:90 to 90:10. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition is a thermoplastic resin composition satisfying the following physical properties (A) to (C): (A) Room temperature impact strength of 3 to 100 kgf m/m (B) low temperature (-40°C) impact strength of 2 to 120 kgf m/m, and (C) The melt flow rate (MFR, 230°C and 2.16 kg) was 0.5 to 200 g/10 min.

Images