KR102335315B1 - Polypropylene based composite - Google Patents

Abstract

The present invention relates to a polypropylene-based composite comprising (A) polypropylene and an olefin-based polymer, wherein the olefin-based polymer has (1) a density (d): 0.85 to 0.89 g/cc; (2) Melt Index (MI, 190°C, 2.16 kg load condition): 0.1 to 15 g/10 min; (3) molecular weight distribution (MWD): 1.0 to 3.0; and (4) the weight average molecular weight (Mw) and Z+1 average molecular weight (Mz+1) satisfy the requirements of satisfying Equation 1, and the polypropylene-based composite of the present invention can exhibit excellent impact strength.

Description

Polypropylene-based composite material {POLYPROPYLENE BASED COMPOSITE}

The present invention relates to a polypropylene-based composite that can exhibit significantly improved impact strength properties at low temperatures along with excellent mechanical strength.

In general, as a composition for automobile interior and exterior parts, a polypropylene-based resin composition containing polypropylene (PP) as a main component and an impact reinforcing material and an inorganic filler has been used.

Until the mid-1990s, before the development of ethylene-α-olefin copolymers polymerized by applying a metallocene catalyst, most polypropylene-based resin compositions, such as EPR (Ethylene Propylene Rubber) or EPDM (ethylene propylene diene rubber) was mainly used as an impact reinforcing material. However, after the appearance of the ethylene-α-olefin copolymer synthesized by the metallocene catalyst, the ethylene-α-olefin copolymer has been used as an impact modifier and is now the mainstream. This is because the polypropylene-based composite material using this material has many advantages such as good formability and low price with balanced physical properties such as impact strength, elastic modulus, and flexural strength.

Polyolefins such as ethylene-α-olefin copolymer synthesized by a metallocene catalyst have a narrow molecular weight distribution and good mechanical properties because their molecular structure is more uniformly controlled than that of a Ziegler-Natta catalyst. Even in the low-density ethylene elastomer polymerized by the metallocene catalyst, since the α-olefin copolymerization monomer is relatively uniformly incorporated into the polyethylene (PE) molecule than that by the Ziegler-Natta catalyst, it is possible to maintain low-density rubber properties while maintaining other mechanical properties. It also has good physical properties.

However, there is a limit in securing impact resistance according to various usage environments, and the development of a polypropylene-based composite that can overcome this limitation is required.

US Patent No. 5,064,802 US Patent No. 6,548,686

An object of the present invention is to provide a polypropylene-based composite that can exhibit significantly improved impact strength properties along with excellent mechanical strength.

The present invention in order to solve the above problems,

Provided is a polypropylene-based composite comprising (A) polypropylene, and (B) an olefin-based polymer satisfying the requirements of (1) to (4) below.

(1) Density (d): 0.85 g/cc to 0.89 g/cc; (2) Melt Index (MI, 190°C, 2.16 kg load condition): 0.1 g/10 min to 15 g/10 min; (3) molecular weight distribution (MWD): 1.0 to 3.0; and (4) the number average molecular weight (Mn) and the z+1 average molecular weight (Mz+1) satisfy Equation 1 below.

[Equation 1]

{Mn/(Mz+1)}×100 > 15

The polypropylene-based composite according to the present invention exhibits an excellent impact strength improvement effect by controlling crystallinity and includes an olefin-based polymer that can be uniformly dispersed in the composite with excellent miscibility with polypropylene, without using a separate additive. It can exhibit significantly improved impact strength properties along with excellent mechanical strength.

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 present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

As used herein, the term "polymer" means a polymer compound prepared by polymerization of monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". "Interpolymer" means a polymer prepared by the polymerization of two or more different types of monomers. The generic term "interpolymer" refers to the term "copolymer", which is commonly used to refer to polymers prepared from two different monomers, as well as "copolymers" commonly used to refer to polymers prepared from three different types of monomers. terpolymer". This includes polymers prepared by polymerization of four or more types of monomers.

In general, polypropylene is used as an interior or exterior material for automobiles such as automobile bumpers, and polyolefin-based polymers are also used as an impact reinforcing material to supplement the low impact strength of polypropylene. Among them, low-density polyolefin-based polymers are used to have high impact strength properties while exhibiting properties such as impact resistance, elastic modulus and tensile properties according to various usage environments, but in this case, the problem of lowering the strength of polypropylene is rather there was.

On the other hand, in the present invention, when the polypropylene-based composite is manufactured, an olefin-based polymer that exhibits excellent impact strength improvement effect and can be uniformly dispersed in the composite with excellent compatibility with polypropylene is used, thereby providing excellent performance without using a separate additive. It can exhibit significantly improved impact strength properties along with mechanical strength.

The polypropylene-based composite material according to an embodiment of the present invention includes (A) polypropylene, and (B) an olefin-based polymer satisfying the requirements of (1) to (4) below.

(1) the density (d) is 0.85 g/cc to 0.89 g/cc, (2) the melt index (Melt Index, MI, 190°C, 2.16 kg load condition) is 0.1 g/10 min to 15 g/10 min; , (3) molecular weight distribution (MWD) is 1.5 to 3.0, (4) number average molecular weight (Mn) and Z+1 average molecular weight (Mz+1) satisfy the following formula (1).

[Equation 1]

{Mn/(Mz+1)}×100 > 15

Hereinafter, each component will be described in detail.

(A) polypropylene

In the polypropylene-based composite material 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 alternately ( alternating) or random, or block copolymers. However, in the present invention, the polypropylene that may overlap with the olefin polymer is excluded, and is a compound different from the olefin polymer.

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 may be 10 min, and more specifically, it may be 10 g/10 min to 50 g/10 min. If the melt index of polypropylene is out of the above range, there is a possibility that a problem may occur during injection molding.

Specifically, in the polypropylene-based composite material 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 measured at 230°C and a load of 2.16 kg. It may be an impact copolymer of 1 g/10min to 90 g/10min, and more specifically, a propylene-ethylene impact copolymer, wherein the impact copolymer is 50 weight based on the total weight of the polypropylene-based composite material % to 90% by weight, more specifically 80% to 90% by weight may be included. When the impact copolymer having such physical properties is included in the above-described content range as polypropylene, strength characteristics, particularly low-temperature strength characteristics, may be improved.

The above-described 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 SEETE™ M1600 manufactured by LG Chem.

In addition, in the polypropylene-based composite material according to an embodiment of the present invention, the polypropylene specifically 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 conditions. , 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 75 wt% to 97 wt% based on the total weight of the polypropylene-based composite , more specifically, may be included in an amount of 85 wt% to 91 wt%. When polypropylene having such physical properties is included in the above-described content range, mechanical strength of the polypropylene composite material 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 in the United States.

(B) Olefin-based polymer

On the other hand, the olefin-based polymer contained in the polypropylene-based composite according to an embodiment of the present invention has the above-described density, melt index, molecular weight distribution, weight average molecular weight (Mw) and Z+1 average of (1) to (4). It is to satisfy the physical property requirements of the relationship of molecular weight (Mz+1) at the same time.

Specifically, the olefin-based polymer according to the present invention exhibits a low density of 0.85 g/cc to 0.90 g/cc when measured according to ASTM D-792, specifically 0.85 g/cc to 0.90 g/cc, more specifically 0.855 g It may have a density of /cc to 0.89 g/cc.

In general, the density of the olefin-based polymer is affected by the type and content of the monomer used during polymerization, the degree of polymerization, and the like. In the present invention, it is possible to introduce a large amount of comonomer by using a metallocene-based catalyst composition including a heterogeneous transition metal compound having a characteristic structure. As a result, the olefin-based polymer according to an embodiment of the present invention has a low density in the range as described above, and as a result, it can exhibit excellent impact strength. When the olefin-based polymer exhibits a density within the above range, the effect of maintaining mechanical properties and improving impact strength according to density control is more remarkable.

In addition, the melt index (MI) affecting the mechanical properties, impact strength, and moldability of the olefin-based polymer can be controlled by adjusting the amount of catalyst used in the polymerization process. In the olefin-based polymer according to an embodiment of the present invention, the melt index is measured at 190 ° C. and 2.16 kg load condition according to ASTM D1238 under a low density condition of 0.85 g/cc to 0.90 g/cc, 0.1 g/ 10 min to 3 g/10 min, specifically 0.2 g/10 min to 2 g/10 min, more specifically 0.25 g/10 min to 1.8 g/10 min. When the melt index of the olefin-based polymer satisfies the above range, excellent impact strength may be exhibited without deterioration of mechanical properties. In consideration of the remarkable effect of improving the balance between mechanical properties and impact strength, the olefin-based polymer may have a melt index of 0.25 g/10 min to 1.8 g/10 min more specifically.

The olefin-based polymer according to the present invention has an ultra-low density, and has a high melting temperature and hardness when it has the same level of density and melt index as compared to a conventional olefin-based polymer, and thus, a polypropylene-based composite material. It is possible to exhibit more excellent tensile strength when included.

In addition, the olefin-based polymer according to an example of the present invention has a weight average molecular weight (Mw) and a number average molecular weight (Mn) ratio (Mw / Mn) (3) molecular weight distribution (MWD; Molecular Weight Distribution) of 1.0 to 3.0, Specifically, it may be 1.5 to 3.0, more specifically 1.8 to 3.0. The olefin-based polymer according to the present invention may exhibit a high molecular weight and a narrow molecular weight distribution.

In addition, in the olefin-based polymer according to an example of the present invention, (4) the weight average molecular weight (Mw) and z+1 average molecular weight (Mz+1) satisfy Equation 1 below.

[Equation 1]

{Mn/(Mz+1)}×100 > 15

The olefin-based polymer included in the polypropylene-based composite according to an example of the present invention is 100 to the value obtained by dividing the number average molecular weight (Mn) by the z+1 average molecular weight (Mz+1) value, which is the average molecular weight focusing on the high molecular weight component. When the multiplied value is 15 or more, it has a larger number average molecular weight (Mn) when it has the same level of z+1 average molecular weight as compared with conventional conventional olefinic polymers.

Mn, Mw and Mz+1 are defined as follows.

When n=1, M=Mw, and when n=3, M=Mz+1.

Mn is a number average molecular weight, Mw is a weight average molecular weight, and Mz+1 is a Z+1 average molecular weight, all terms referring to average molecular weight.

In addition, (B) the olefin-based polymer included in the polypropylene-based composite according to an example of the present invention may further satisfy (5) the density and melting temperature (Tm) of Equation 2 below.

[Equation 2]

Tm = a×density- b (2,350<a<2,500, 1,900<b<2,100)

In addition, (B) the olefin-based polymer included in the polypropylene-based composite according to an example of the present invention may further satisfy (6) hardness and melting temperature (Tm) of 1.0 < hardness / Tm < 1.3.

In addition, the (B) olefin-based polymer included in the polypropylene-based composite according to an example of the present invention may satisfy (7) a weight average molecular weight (Mw): 10,000 g/mol to 500,000 g/mol, specifically 20,000 g /mol to 300,000 g/mol, more specifically, 50,000 g/mol to 200,000 g/mol may be satisfied. In the present invention, the weight average molecular weight (Mw) is a polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).

In addition, the (B) olefin-based polymer included in the polypropylene-based composite according to an example of the present invention (8) may have a number average molecular weight (Mn) of 8,000 g/mol to 300,000 g/mol, specifically 10,000 g/mol mol to 200,000 g/mol, more specifically 20,000 g/mol to 80,000 g/mol.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).

In addition, the (B) olefin-based polymer included in the polypropylene-based composite according to an example of the present invention may satisfy (9) Z+1 average molecular weight (Mz+1): 50,000 g/mol to 1,500,000 g/mol, Specifically, 80,000 g/mol to 1,000,000 g/mol, more specifically 100,000 g/mol to 900,000 g/mol may be satisfied. When the olefin-based polymer satisfies the Z+1 average molecular weight (Mz+1) in the above range, it contains an appropriate high molecular weight component and exhibits excellent hardness, and the polypropylene-based composite including the same can exhibit improved impact strength.

In general, the density of the olefin-based polymer is affected by the type and content of the monomer used during polymerization, the degree of polymerization, and the like. The olefin-based polymer of the present invention is polymerized using a catalyst composition including two types of transition metal compounds having a characteristic structure, and a large amount of comonomer can be introduced. has a low density of

In one example of the present invention, the olefin-based polymer may have a melting temperature (Tm) obtained from a DSC curve obtained by measuring with a differential scanning calorimeter (DSC) of 100° C. or less, specifically 90° C. or less, more specifically 10° C. to It may be 80°C.

Further, in an example of the present invention, the olefin-based polymer may have a hardness (Shore A) of 20 to 80, specifically 30 to less than 80, and more specifically 35 to 75. Since the olefin-based polymer satisfies the hardness value, the polypropylene-based composite including the same may exhibit improved impact strength.

In one example of the present invention, the olefin-based polymer may exhibit a high hardness (Shore A) at the same level of density and melt index value as compared to a conventional conventional olefin-based polymer, and thus a polypropylene-based polymer including the same Composites can exhibit improved impact strength.

The olefin-based polymer is an olefin-based monomer, specifically, an alpha-olefin-based monomer, a cyclic olefin-based monomer, a diene olefin-based monomer, a triene olefin-based monomer, and a styrenic monomer, or any one homopolymer selected from It may be a copolymer of more than one species. More specifically, the olefin-based polymer may be a copolymer of ethylene and an alpha-olefin having 3 to 12 carbon atoms or 3 to 10 carbon atoms.

The alpha-olefin comonomer is 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, 1-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 -It may include any one or a mixture of two or more selected from the group consisting of -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

More specifically, the olefin copolymer according to an example of the present invention may be a copolymer of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, or ethylene and 1-octene. have.

When the olefin-based polymer is a copolymer of ethylene and alpha-olefin, the amount of the alpha-olefin is 90 wt% or less, more specifically 70 wt% or less, even more specifically 5 wt% to 60 wt% based on the total weight of the copolymer. % by weight. When included in the above range, it is easy to implement the above-described physical properties,

The olefin-based polymer according to an embodiment of the present invention having the above physical properties and structural characteristics is prepared through a continuous solution polymerization reaction in the presence of a metallocene catalyst composition including one or more transition metal compounds in a single reactor can be Accordingly, in the olefin-based polymer according to an embodiment of the present invention, a block is not formed in which two or more repeating units derived from any one of the monomers constituting the polymer in the polymer are linearly connected. That is, the olefin-based polymer according to the present invention does not contain a block copolymer, and is selected from the group consisting of a random copolymer, an alternating copolymer, and a graft copolymer. may be, and more specifically, may be a random copolymer.

Specifically, the olefin-based copolymer of the present invention can be obtained by a manufacturing method comprising the step of polymerizing an olefin-based monomer in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 below.

However, in the preparation of the olefin-based polymer according to an embodiment of the present invention, the scope of the structure of the following transition metal compound is not limited to a specific disclosed form, and all modifications and equivalents included in the spirit and scope of the present invention or substitutes.

[Formula 1]

In Formula 1,

R ₁ is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms;

R _2a to R _2e are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms,

R ₃ is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 6 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkyl amido having 1 to 20 carbon atoms; aryl amido having 6 to 20 carbon atoms; alkylidene having 1 to 20 carbon atoms; or halogen, alkyl having 1 to 20 carbons, cycloalkyl having 3 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, and aryl having 6 to 20 carbons Substituted with one or more selected from the group consisting of is phenyl,

R ₄ to R ₉ are each independently hydrogen; silyl; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other among R ₆ to R ₉ may be connected to each other to form a ring,

Q is Si, C, N, P or S;

M is a group 4 transition metal,

X ₁ and X ₂ are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; arylamino having 6 to 20 carbon atoms; or an alkylidene having 1 to 20 carbon atoms.

In an example of the present invention, in the transition metal compound of Formula 1,

wherein R ₁ is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms,

said R _2a to R _2e are each independently hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; alkoxy having 1 to 12 carbon atoms; or phenyl,

wherein R ₃ is hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 13 carbon atoms; arylalkyl having 7 to 13 carbon atoms; Or it may be phenyl substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, and phenyl,

The R ₄ to R ₉ are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms,

two or more adjacent to each other among R ₆ to R ₉ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms,

Q may be Si,

M may be Ti,

The X ₁ and X ₂ are each independently hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; alkylaryl having 7 to 13 carbon atoms; arylalkyl having 7 to 13 carbon atoms; alkylamino having 1 to 13 carbon atoms; arylamino having 6 to 12 carbon atoms; Or it may be an alkylidene having 1 to 12 carbon atoms.

In addition, in another example of the present invention, in the transition metal compound of Formula 1,

wherein R ₁ is hydrogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkoxy having 1 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; arylalkoxy having 7 to 13 carbon atoms; alkylaryl having 7 to 13 carbon atoms; Or it may be an arylalkyl having 7 to 13 carbon atoms,

said R _2a to R _2e are each independently hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; alkoxy having 1 to 12 carbon atoms; or phenyl,

wherein R ₃ is hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; alkylaryl having 7 to 13 carbon atoms; arylalkyl having 7 to 13 carbon atoms; phenyl; Or it may be phenyl substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, and phenyl,

The R ₄ to R ₉ are each independently hydrogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; alkylaryl having 7 to 13 carbon atoms; Or it may be an arylalkyl having 7 to 13 carbon atoms,

Two or more adjacent to each other among R ₆ to R ₉ may be connected to each other to form an aliphatic ring having 5 to 12 carbon atoms or an aromatic ring having 6 to 12 carbon atoms,

The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms,

Q may be Si,

M may be Ti,

The X ₁ and X ₂ are each independently hydrogen; halogen; an alkyl group having 1 to 12 carbon atoms; Or it may be alkenyl having 2 to 12 carbon atoms.

In addition, in another example of the present invention, in the transition metal compound of Formula 1,

Wherein R ₁ may be hydrogen or alkyl having 1 to 12 carbon atoms,

said R _2a to R _2e are each independently hydrogen; alkyl having 1 to 12 carbon atoms; Or it may be an alkoxy having 1 to 12 carbon atoms,

wherein R ₃ is hydrogen; alkyl having 1 to 12 carbon atoms; or phenyl,

The R ₄ and R ₅ are each independently hydrogen; Or it may be an alkyl having 1 to 12 carbon atoms,

The R ₆ to R ₉ may each independently be hydrogen or methyl,

Q may be Si,

M may be Ti,

The X ₁ and X ₂ may each independently be hydrogen or an alkyl having 1 to 12 carbon atoms.

The compound represented by Formula 1 may be any one of compounds represented by Formulas 1-1 to 1-10 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

In addition, it may be a compound having various structures within the range defined in Formula 1 above.

The transition metal compound represented by Formula 1 has a metal site connected by a cyclopentadienyl ligand into which tetrahydroquinoline is introduced, and thus the Cp-MN angle is structurally narrow, and the X ₁ -MX ₂ angle that the monomer approaches is wide. features to retain. In addition, Cp, tetrahydroquinoline, nitrogen and metal sites are sequentially linked by a ring bond to form a more stable and rigid pentagonal ring structure. Therefore, when these compounds are _{activated by reacting them with a cocatalyst such as methylaluminoxane or B(C 6} F ₅ ) ₃ and then applied to olefin polymerization, characteristics such as high activity, high molecular weight, and high copolymerizability can be obtained even at high polymerization temperatures. It is possible to polymerize the olefinic polymer having

Each of the substituents defined in the present specification will be described in detail as follows.

As used herein, the term 'hydrocarbyl group' is, unless otherwise stated, the number of carbon atoms consisting only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl. It means a monovalent hydrocarbon group of 1 to 20.

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

The term 'alkyl' as used herein, unless otherwise specified, refers to a straight-chain or branched hydrocarbon residue.

As used herein, the term 'alkenyl' refers to a straight-chain or branched alkenyl group, unless otherwise noted.

The branched chain is alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.

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

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group means an alkyl group substituted by the aryl group.

The ring (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 ring atoms and containing at least one hetero atom, and may be a single ring or a condensed ring of two or more rings. In addition, the heterocyclic group may be unsubstituted or substituted with an alkyl group. Examples thereof include indoline and tetrahydroquinoline, but the present invention is not limited thereto.

The alkyl amino group 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.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is limited to these examples only. no.

The transition metal compound of Formula 1 and the transition metal compound of Formula 2 have a density of 0.89 g/cc or less, more specifically, a density of 0.89 g/cc or less, because a large amount of alpha-olefin as well as low-density polyethylene can be introduced due to the structural characteristics of the catalyst. It is possible to prepare a low-density polyolefin copolymer at a level of 0.85 g/cc to 0.89 g/cc.

The transition metal compound of Formula 1 may be prepared from a ligand compound represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ₁ and R ₁₀ are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms;

R _2a to R _2e are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms,

R ₃ is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 6 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkyl amido having 1 to 20 carbon atoms; aryl amido having 6 to 20 carbon atoms; alkylidene having 1 to 20 carbon atoms; or halogen, alkyl having 1 to 20 carbons, cycloalkyl having 3 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, and aryl having 6 to 20 carbons Substituted with one or more selected from the group consisting of is phenyl,

R ₄ to R ₉ are each independently hydrogen; silyl; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other among R ₆ to R ₉ may be connected to each other to form a ring,

Q is Si, C, N, P or S.

_{In the ligand compound, definitions of R 1} to R ₉ in the compound represented by Formula 2 may be the same as those in the compound represented by Formula 1 as a transition metal compound.

The compound represented by Chemical Formula 2 may be any one of compounds represented by the following Chemical Formulas 2-1 to 2-10.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

The ligand compound represented by Formula 2 of the present invention can be prepared as shown in Scheme 1 below.

[Scheme 1]

In Scheme 1, R ₁ to R ₁₀ and Q are as defined in Formula 2 above.

Specifically, the method for preparing the ligand compound of Formula 2 includes a) reacting a compound represented by the following [Formula 4] with a compound represented by the following [Formula 5] to prepare a compound represented by the following [Formula 3] step; and b) reacting a compound represented by the following [Formula 3] with a compound represented by the following [Formula 6] to prepare a compound represented by the following [Formula 2].

[Formula 4]

[Formula 5]

[Formula 3]

[Formula 6]

R ₁ R ₁₀ NH

[Formula 2]

In the above formula, R ₁ to R ₁₀ and Q are as defined in Formula 2 above.

In the step a) preparing a compound represented by the following [Formula 3] by reacting a compound represented by the following [Formula 4] with a compound represented by the following [Formula 5], the compound represented by the Formula 4 and the Formula The compound represented by 5 may be reacted in a molar ratio of 1:0.8 to 1:5.0, specifically, in a molar ratio of 1:0.9 to 1:4.0, more specifically, in a molar ratio of 1:1 to 1:3.0.

In addition, the reaction may be carried out at a temperature range of -80 °C to 140 °C for 1 hour to 48 hours.

On the other hand, b) in the step of preparing a compound represented by the following [Formula 2] by reacting the compound represented by the following [Formula 3] with the compound represented by the following [Formula 6], the compound represented by the formula 3 and the The compound represented by Formula 6 may be reacted in a molar ratio of 1:0.8 to 1:5.0, specifically, in a molar ratio of 1:0.9 to 1:4.5, and more specifically, in a molar ratio of 1:1 to 1:4.0.

The compound represented by Chemical Formula 4 may be prepared as shown in Scheme 2 below.

[Scheme 2]

In Scheme 2, R ₄ to R ₉ are as defined in Formula 1 or Formula 2 above.

The transition metal compound represented by Formula 1 of the present invention can be prepared as shown in Scheme 3 below using the ligand compound represented by Formula 2 above.

[Scheme 3]

In the above formula, R ₁ to R ₁₀ , Q, M, X ₁ and X ₂ are as defined in Formula 1 or Formula 2 above.

According to an embodiment of the present invention, the transition metal compound represented by Formula 1 may be in a form in which a Group 4 transition metal is coordinated using the compound represented by Formula 2 as a ligand.

Specifically, as shown in Scheme 3, the compound represented by Formula 2 is reacted with a compound represented by Formula 7 below, which is a metal precursor, and an organolithium compound, and the compound represented by Formula 2 is used as a ligand for a Group 4 transition metal The coordinated transition metal compound of Formula 1 can be obtained.

[Formula 2]

[Formula 7]

M(X _One X ₂ ) ₂

[Formula 1]

In the above formula, R ₁ to R ₁₀ , Q, M, X ₁ and X ₂ are as defined in Formula 1 above.

In Scheme 3, the organolithium compound is, for example, n-butyllithium, sec-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexyllithium, allyllithium, vinyllithium, phenyllithium and benzyllithium. One or more may be selected from the group consisting of.

The compound represented by Formula 2 and the compound represented by Formula 7 may be mixed in a molar ratio of 1: 0.8 to 1: 1.5, preferably 1: 1.0 to 1: 1.1.

In addition, the organolithium compound may be used in an amount of 180 parts by weight to 250 parts by weight based on 100 parts by weight of the compound represented by Formula 2.

The reaction may be carried out at a temperature range of -80 °C to 140 °C for 1 hour to 48 hours.

The transition metal compound of Formula 1 may be mixed alone or in the form of a composition further comprising one or more of the promoter compounds represented by Formula 8, Formula 9, and Formula 10 in addition to the transition metal compound of Formula 1 , can be used as a catalyst for polymerization reactions.

[Formula 8]

-[Al(R ₁₁ )-O] _a -

[Formula 9]

A(R ₁₁ ) ₃

[Formula 10]

[LH] ⁺ [W(D) ₄ ] ^- or [L] ⁺ [W(D) ₄ ] ^-

In Formulas 8 to 10,

R ₁₁ may be the same as or different from each other, and are each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

A is aluminum or boron,

D is each independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, wherein the substituents are halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms and at least one selected from the group consisting of aryloxy having 6 to 20 carbon atoms,

H is a hydrogen atom,

L is a neutral or cationic Lewis acid,

W is a group 13 element,

a is an integer greater than or equal to 2;

Examples of the compound represented by Formula 8 include alkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and two or more kinds of the alkylaluminoxane are mixed and modified alkylaluminoxane, and specifically may be methylaluminoxane and modified methylaluminoxane (MMAO).

Examples of the compound represented by Formula 9 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , 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, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc. are included, and specifically, it may be selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

Examples of the compound represented by the formula (10) include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra (o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N -Diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, dimethyl Anilinium tetrakis(pentafluorophenyl)borate, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, tri Propylammonium tetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum , tributylammoniumtetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentatenttraphenylaluminum, triphenyl Phosphonium tetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl) ) boron or triphenylcarboniumtetrapentafluorophenylboron.

The catalyst composition, as a first method, 1) contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 8 or Formula 9 to obtain a mixture; and 2) adding the compound represented by Formula 10 to the mixture.

In addition, as a second method, the catalyst composition may be prepared by contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 8.

In the case of the first method among the methods for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 8 or Formula 9 may be 1/5,000 to 1/2, and specifically may be 1/1,000 to 1/10, and more specifically, 1/500 to 1/20. When the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 8 or Formula 9 exceeds 1/2, the amount of the alkylating agent is very small, and there is a problem that the alkylation of the metal compound cannot proceed completely, , when the molar ratio is less than 1/5,000, the metal compound is alkylated, but due to a side reaction between the remaining excess alkylating agent and the activator, which is the compound of Formula 10, there is a problem in that the activation of the alkylated metal compound cannot be completed. . In addition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 10 may be 1/25 to 1, specifically 1/10 to 1, and more specifically 1/5 to can be 1. When the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 10 exceeds 1, the amount of the activator is relatively small, so the activation of the metal compound is not completely achieved, and thus the activity of the catalyst composition may fall, and if the molar ratio is less than 1/25, the metal compound is fully activated, but the unit price of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with an excess of the remaining activator.

In the case of the second method among the methods for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1/Compound represented by Formula 8 may be 1/10,000 to 1/10, and specifically 1/5,000 It may be from 1/100 to 1/100, and more specifically, from 1/3,000 to 1/500. When the molar ratio is greater than 1/10, the amount of the activator is relatively small, so the activation of the metal compound may not be completely achieved, and thus the activity of the resulting catalyst composition may be reduced. If it is less than 1/10,000, the activation of the metal compound is completely achieved, but the unit cost of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with the remaining excess activator.

When preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene or toluene may be used as the reaction solvent.

In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a supported form on a carrier.

The carrier may be used without any particular limitation as long as it is used as a carrier in a metallocene-based catalyst. Specifically, the carrier may be silica, silica-alumina or silica-magnesia, and any one or a mixture of two or more thereof may be used.

Among them, when the carrier is silica, since the functional group of the silica carrier and the metallocene compound of Formula 1 chemically forms a bond, there is almost no catalyst released from the surface during the olefin polymerization process. As a result, it is possible to prevent the occurrence of fouling in which the reactor wall surface or polymer particles are agglomerated during the manufacturing process of the olefin-based polymer. In addition, the olefin-based polymer prepared in the presence of the catalyst including the silica carrier has excellent particle shape and apparent density of the polymer.

More specifically, the carrier may be high-temperature dried silica or silica-alumina containing a siloxane group having high reactivity on the surface through a method such as high-temperature drying.

The carrier may further include an oxide, carbonate, sulfate or nitrate component such as _{Na 2} O, K ₂ CO ₃ , BaSO ₄ or Mg(NO ₃ ) _{2 .}

The polymerization reaction for polymerizing the olefinic monomer may be accomplished by a conventional process applied to polymerization of the olefinic monomer, such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, or emulsion polymerization.

The polymerization reaction of the olefin monomer may be performed under an inert solvent, and examples of the inert solvent include benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, but not limited thereto.

The polymerization of the olefin-based polymer may be performed by reacting at a temperature of about 25° C. to about 500° C. and ^{a pressure of about 1 kgf/cm 2} to about 100 kgf/cm ^{2 .}

Specifically, the polymerization of the polyolefin may be carried out at a temperature of about 25 °C to about 500 °C, specifically 80 °C to 250 °C, more preferably, it may be carried out at a temperature of 100 °C to 200 °C. In addition, the reaction pressure during polymerization is 1 kgf/cm ² to 150 kgf/cm ² , preferably 1 kgf/cm ² to 120 kgf/cm ² , more preferably 5 kgf/cm ² to 100 kgf/cm ² It may be.

On the other hand, when the polypropylene-based composite material according to an embodiment of the present invention having the above-described configuration is applied to a rubber composition, each component is added in an appropriate amount to satisfy the use and physical properties required accordingly. may include Specifically, in the present invention, the polypropylene-based composite may include 5 wt% to 40 wt% of the (B) olefin-based polymer, and specifically 10 wt% to 30 wt%.

When the content of the olefin-based polymer is less than the mixing ratio, there is a fear that impact strength may be lowered, and if it exceeds the mixing ratio, tensile strength and hardness may be reduced. It can be considered that the improvement effect is remarkable according to the control of the mixing ratio of the polypropylene and the olefin-based polymer.

The polypropylene-based composite according to an embodiment of the present invention may optionally further include an inorganic filler together with the polypropylene and the olefin-based polymer to improve the mechanical properties of the polypropylene-based composite.

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, the flaky filler may 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 the strength characteristics and molding processability of the polypropylene composite.

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, more specifically 7 μm to 15 μm. If the average particle diameter of the inorganic filler is less than 1 μm, it is difficult to uniformly disperse when mixed with polypropylene and olefin-based polymer due to aggregation between the inorganic filler particles, and as a result, the effect of improving the mechanical properties of the polypropylene-based composite agent may be insignificant. In addition, when the average particle diameter of the inorganic filler exceeds 20 μm, there is a risk of deterioration of the physical properties of the rubber composition due to the deterioration of 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 polypropylene. If the content of the inorganic filler in the polypropylene composite is less than 0.1 parts by weight based on 100 parts by weight of polypropylene, the improvement effect due to the inclusion of the inorganic filler is insignificant, and if it exceeds 40 parts by weight, the workability of the polypropylene composite may be reduced. 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 polypropylene composite.

The polypropylene-based composite material according to an embodiment of the present invention satisfying the composition and content conditions as described above may be prepared by adding polypropylene and optionally an inorganic filler to an olefin-based polymer and then heat-treating. 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 performed using various compounding machines such as a conventional twin-screw extruder, a single-screw extruder, a roll-mill, a kneader, or a Banbury mixer. can be performed.

The polypropylene composite according to an embodiment of the present invention produced according to the manufacturing method as described above, by using an optimally combined heterogeneous olefinic polymer to improve the impact strength of the polypropylene composite, The acidity can be further increased, and as a result, the impact strength can be improved without deterioration in mechanical properties such as tensile strength of the polypropylene composite.

^{Specifically, the polypropylene composite material may have a maximum tensile strength of 170 kgf/cm 2} to 200 kgf/cm ² when measuring a maximum tensile strength according to ASTM D638 (condition: 50 mm/min). In addition, the polypropylene-based composite material has a low-temperature impact strength of 5 kgf·m/m or more, specifically 5 kgf·m/m to 10 kgf·m/m/ m, more specifically 5.5 kgf·m/m to 9 kgf·m/m. In addition, the polypropylene-based composite material has an impact strength of 40 kgf·m/m or more, specifically 50 kgf·m/m to 70 kgf·m/m/ can be m.

Accordingly, the polypropylene-based composite material according to an embodiment of the present invention is hollow in various fields and uses, such as materials for automobiles, electric wires, toys, textiles, or medical products, for packaging, construction, and daily use. It is useful for molding, extrusion 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 that it can be usefully used for interior and exterior parts of automobiles can

According to another embodiment of the present invention, there is provided a molded article and an automobile part manufactured using a polypropylene-based composite 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 and exterior materials for automobiles.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are only illustrative of the present invention and the scope of the present invention is not limited to the following examples.

Catalyst Preparation Example 1: Preparation of transition metal compound 1

<Synthesis of N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silanamine>

Chloro -1-(1,2-dimethyl-3H- Benzo[b]cyclopenta[d]thiophene -3-yl)-1,1-( methyl ) (phenyl) silane preparation

In a 250 mL Schlenk flask, put 10 g (1.0 eq, 49.925 mmol) of 1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene and 100 mL of THF, and 22 mL of n-BuLi (1.1 eq, 54.918 mmol, 2.5 M in hexane) was added dropwise at -30°C, followed by stirring at room temperature for 3 hours. The stirred Li-complex THF solution was cannulated at -78°C in a Schlenk flask containing 8.1 mL (1.0 eq, 49.925 mmol) of dichloro(methyl)(phenyl)silane and 70 mL of THF, followed by stirring at room temperature overnight. After stirring, the mixture was dried in vacuo, and extracted with 100 mL of hexane.

N- tert -Butyl-1-(1,2-dimethyl-3H- Benzo[b]cyclopenta[d]thiophene -3-yl)-1,1- ( methyl ) (phenyl) silanamine preparation

t-BuNH in 100 mL of extracted chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silane hexane solution ₂ 42 mL (8 eq, 399.4 mmol) was added at room temperature, followed by stirring at room temperature overnight. After stirring, the mixture was dried in vacuo, and extracted with 150 mL of hexane. After solvent drying, 13.36 g (68 %, dr = 1:1) of a yellow solid was obtained.

¹ H NMR (CDCl ₃ , 500 MHz): δ 7.93 (t, 2H), 7.79 (d,1H), 7.71 (d,1H), 7.60 (d, 2H), 7.48 (d, 2H), 7.40-7.10 (m, 10H, aromatic), 3.62 (s, 1H), 3.60 (s, 1H), 2.28 (s, 6H), 2.09 (s, 3H), 1.76 (s, 3H), 1.12 (s, 18H), 0.23 (s, 3H), 0.13 (s, 3H)

In a 100 mL Schlenk flask, add 4.93 g (12.575 mmol, 1.0 eq) of the ligand compound of Formula 2-4 and 50 mL (0.2M) of toluene, and 10.3 mL (25.779 mmol, 2.05 eq, 2.5M in hexane) of n-BuLi. was added dropwise at -30°C, followed by stirring at room temperature overnight. After stirring, 12.6 mL (37.725 mmol, 3.0 eq, 3.0 M in diethyl ether) of MeMgBr was added dropwise, and then TiCl ₄ 13.2 mL (13.204 mmol, 1.05 eq, 1.0 M in toluene) was added in this order and stirred at room temperature overnight. . After stirring, the mixture was dried in vacuo, extracted with 150 mL of hexane, and the solvent was removed to 50 mL, and then 4 mL (37.725 mmol, 3.0eq) of DME was added dropwise, followed by stirring at room temperature overnight. After vacuum drying again, the mixture was extracted with 150 mL of hexane. After solvent drying, 2.23 g (38 %, dr = 1:0.5) of a brown solid was obtained.

¹ H NMR (CDCl ₃ , 500 MHz): δ 7.98 (d, 1H), 7.94 (d, 1H), 7.71 (t, 6H), 7.50-7.30 (10H), 2.66 (s, 3H), 2.61 (s) , 3H), 2.15 (s, 3H), 1.62 (s, 9H), 1.56 (s, 9H), 1.53 (s, 3H), 0.93 (s, 3H), 0.31 (s, 3H), 0.58 (s, 3H), 0.51 (s, 3H), -0.26 (s, 3H), -0.39 (s, 3H)

Catalyst Preparation Example 2: Preparation of transition metal compound 2

(1) 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8-(2,3,4,5- Preparation of tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline)

(i) Preparation of lithium carbamate

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a shlenk flask. The Schlenk flask was immersed in a -78°C low-temperature bath made of dry ice and acetone and stirred for 30 minutes. Then, n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was injected into a syringe under a nitrogen atmosphere, and a pale yellow slurry was formed. Then, after stirring the flask for 2 hours, the temperature of the flask was raised to room temperature while removing the butane gas produced. The flask was again immersed in a low temperature bath at -78° C. to lower the temperature, and then CO ₂ gas was introduced. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler and the temperature was raised to room temperature while removing carbon dioxide gas. After that, excess CO ₂ gas and solvent were removed under vacuum. After moving the flask to a dry box, pentane was added, stirred vigorously, and filtered to obtain lithium carbamate, a white solid compound. The white solid compound is coordinated with diethyl ether. In this case, the yield is 100%.

¹ H NMR(C ₆ D ₆ , C ₅ D ₅ N): δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH ₂ ), 2.34 (br s, 2H) , quin-CH ₂ ), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quin-CH ₂ ), 6.76 (br d, J = 5.6 Hz, 1H, quin-CH ) ppm

¹³ C NMR (C ₆ D ₆ ): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09 (C=O) ppm

(ii) Preparation of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was placed in a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were sequentially added. The Schlenk flask was immersed in a low temperature bath at -20°C made with acetone and a small amount of dry ice and stirred for 30 minutes, and then t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture changed to red. Stirring was continued for 6 hours while maintaining -20°C. CeCl ₃ ·2LiCl solution (129 mL, 0.33 M, 42.60 mmol) dissolved in tetrahydrofuran and tetramethylcyclopentynone (5.89 g, 42.60 mmol) were mixed in a syringe, and then put into a flask under a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature, and after 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Then, after adding water (15 mL) to the flask, ethyl acetate was added thereto and filtered to obtain a filtrate. After the filtrate was transferred to a separatory funnel, hydrochloric acid (2 N, 80 mL) was added, and the mixture was shaken for 12 minutes. Then, after neutralization by adding a saturated aqueous sodium hydrogen carbonate solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture, filtered, and the filtrate was taken to remove the solvent. The obtained filtrate was purified by column chromatography using a solvent of hexane and ethyl acetate (v/v, 10:1) to obtain a yellow oil. The yield was 40%.

¹ H NMR(C ₆ D ₆ ): δ 1.00 (br d, 3H, Cp-CH ₃ ), 1.63 - 1.73 (m, 2H, quin-CH ₂ ), 1.80 (s, 3H, Cp-CH ₃ ), 1.81 (s, 3H, Cp-CH ₃ ), 1.85 (s, 3H, Cp-CH ₃ ), 2.64 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 2.84 - 2.90 (br, 2H, quin -CH ₂ ), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, NH), 6.77 (t, J = 7.2 Hz, 1H, quin-CH), 6.92 (d, J = 2.4 Hz, 1H, quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm

(2) [(1,2,3,4- tetrahydroquinoline -8-day) Tetramethylcyclopentadienyl - η ⁵ , κ -N] titanium dimethyl ([(1,2,3,4- Tetrahydroquinolin Preparation of -8-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl)

(i) Preparation of [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η ⁵ , κ -N]dilithium compound

8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8.07 g) prepared through step (1) in a dry box , 32.0 mmol) and 140 mL of diethyl ether were placed in a round flask, the temperature was lowered to -30°C, and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added with stirring. The reaction was carried out for 6 hours while raising the temperature to room temperature. After that, it was filtered while washing with diethyl ether several times to obtain a solid. A vacuum was applied to remove the remaining solvent to obtain a dilithium compound (9.83 g) as a yellow solid. The yield was 95%.

¹ H NMR(C ₆ D ₆ , C ₅ D ₅ N): δ 2.38 (br s, 2H, quin-CH ₂ ), 2.53 (br s, 12H, Cp-CH ₃ ), 3.48 (br s, 2H, quin-CH ₂ ), 4.19 (br s, 2H, quin-CH ₂ ), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs) , 1H, quin-CH) ppm

(ii) (1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- η ⁵ , κ -N] Preparation of titanium dimethyl

In a dry box, TiCl ₄ ·DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were placed in a round flask, and while stirring at -30°C, MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added thereto. After stirring for 15 minutes, the [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- ηη ⁵ , κ -N]dilithium compound prepared in step (i) ( 5.30 g, 15.76 mmol) was placed in a flask. The mixture was stirred for 3 hours while raising the temperature to room temperature. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, and filtered to obtain a filtrate. When pentane was removed by vacuum, a dark brown compound (3.70 g) was obtained. The yield was 71.3%.

¹ H NMR(C ₆ D ₆ ): δ 0.59 (s, 6H, Ti-CH ₃ ), 1.66 (s, 6H, Cp-CH ₃ ), 1.69 (br t, J = 6.4 Hz, 2H, quin-CH ₂ ), 2.05 (s, 6H, Cp-CH ₃ ), 2.47 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 4.53 (m, 2H, quin-CH ₂ ), 6.84 (t, J = 7.2 Hz, 1H, quin-CH), 6.93 (d, J =7.6 Hz, quin-CH), 7.01 (d, J =6.8 Hz, quin-CH) ppm

¹³ C NMR (C ₆ D ₆ ): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm

Example Preparation Example 1

After the 1.5L autoclave continuous process reactor was charged with hexane solvent (5 kg/h) and 1-butene (0.35 kg/h), the temperature at the top of the reactor was preheated to 150° C. Triisobutylaluminum compound (1.3 mmol/min) ), the transition metal compound 1 (1.05 μmol/min) obtained in Preparation Example 1, and dimethylanilinium tetrakis(pentafluorophenyl) borate cocatalyst (0.6 μmol/min) were simultaneously introduced into the reactor as a catalyst. , ethylene (0.87 kg/h) was introduced into the autoclave reactor, and the copolymer was obtained by carrying out a copolymerization reaction by maintaining it at 150° C. for at least 30 minutes in a continuous process at a pressure of 89 bar. was measured.

Example Preparation 2

As shown in Table 2 below, a copolymer was prepared in the same manner as in Preparation Example 1, except that the content of each material was different.

Comparative Preparation Examples 1 and 2

The same method as in Preparation Example 1, except that the transition metal compound 2 obtained in Preparation Example 2 was used instead of the transition metal compound 1 as a catalyst, and the content of each material was changed as shown in Table 1 below. to prepare a copolymer.

density
(g/cc) MI
(dg/min) C2
(kg/h) C6
(kg/h) 1-C4
(kg/h) Cat.
(μmol/min) Co-cat.
(μmol/min) TiBAl
(mol/min) RT
(℃) comparison
Preparation Example 1 0.864 6.3. 0.87 5.0 0.65 1.95 0.06 0.85 170.3 comparison
Preparation 2 0.862 1.3 0.87 5.00 0.52 1.56 0.6 0.65 145.8 practice
Preparation Example 1 0.863 5.7 0.87 5.00 0.35 1.05 0.6 1.3 149.9 practice
Preparation 2 0.862 1.2 0.87 5.00 0.25 0.75 0.6 1.05 135.5

In Table 1, MI is melt index, Cat is catalyst (transition metal oxide), Co-cat is dimethylanilinium tetrakis(pentafluorophenyl) borate as co-catalyst, TiBAl is triisobutylaluminum, RT is reaction temperature indicates.

Example 1: Preparation of polypropylene-based composites

To 20 parts by weight of the olefin copolymer prepared in Preparation Example 1, 60 parts by weight of impact copolymer polypropylene (SEETE M1600, LG Chem) having a melt index of 25 g/10 min and talc (KCNAP-400™, Kotsu Corporation) (Average particle diameter (D ₅₀ ) = 11.0 μm) 20 parts by weight was added, and 0.01 parts by weight of tris(2,4-di-tert-butylphenyl)phosphite (A0168) as an antioxidant was added, and then using a twin-screw extruder. A polypropylene-based composite compound in the form of pellets was prepared by melt-kneading. At this time, the twin screw extruder had a diameter of 25Φ, a ratio of diameter and length of 40, a barrel temperature of 160°C to 210°C, a screw rotation speed of 250 rpm, and an extrusion amount of 25 kr/hr.

Example 2: Preparation of polypropylene-based composites

A polypropylene-based composite was prepared in the same manner as in Example 1, except that the olefin copolymer prepared in Preparation Example 2 was used instead of the olefin copolymer prepared in Preparation Example 1.

Comparative Example 1: Preparation of polypropylene-based composites

A polypropylene-based composite was prepared in the same manner as in Example 1, except that the olefin-based polymer prepared in Comparative Preparation Example 1 was used instead of the olefin-based polymer in Example 1.

Comparative Example 2: Preparation of polypropylene-based composites

A polypropylene-based composite was prepared in the same manner as in Example 1, except that the olefin-based polymer prepared in Comparative Preparation Example 2 was used instead of the olefin-based polymer in Example 1.

Experimental Example 1: Evaluation of Physical Properties of Olefin-Based Polymers (I)

The physical properties of the olefin-based copolymers prepared in Examples 1 and 2 and Comparative Preparation Examples 1 and 2 were evaluated according to the following method, and are shown in Table 2 below.

- Density of the polymer; Measured by ASTM D-792.

- The melt index (MI) of the polymer was measured by ASTM D-1238 (Condition E, 190°C, 2.16 kg load).

- weight average molecular weight (Mw, g/mol), number average molecular weight (Mn, g/mol), Z+1 average molecular weight (Mz+1, g/mol), and molecular weight distribution (MWD): gel permeation chromatography ( The weight average molecular weight (Mw, g/mol), number average molecular weight (Mn, g/mol), and Z+1 average molecular weight (Mz+1) were respectively measured using GPC: gel permeation chromatography, and the weight The molecular weight distribution was calculated by dividing the average molecular weight by the number average molecular weight.

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

Density (g/cc) MI
(dg/min) Mn
(g/mol) Mw
(g/mol) Mz+1
(g/mol) MWD

*100

*100 Hardness
(Shore A) Comparative Preparation Example 1 0.864 6.3. 29090 66491 206247 2.29 14.1 47.5 comparison
Preparation 2 0.862 1.3 47691 106205 331126 2.23 14.4 45.4 practice
Preparation Example 1 0.863 5.7 33336 69738 180383 2.09 18.5 48.2 practice
Preparation 2 0.862 1.2 55426 112552 331726 2.03 16.7 47.3

In Table 1, MI represents melt index and MWD represents molecular weight distribution.

Experimental Example 2: Evaluation of physical properties of polypropylene-based composites

In order to confirm the physical properties of the polypropylene-based composites prepared in Examples 1 and 2 and Comparative Examples 1 and 2, a specimen was prepared by injection molding the polypropylene-based composite at a temperature of 200° C. using an injection machine, and a constant temperature After standing in a humidity room for 1 day, the density of the polymer, the melt index of the polymer, the tensile strength, the flexural strength and the flexural modulus, and the low temperature and room temperature impact strength were measured. The physical properties of the prepared specimens are shown in Table 3 below.

- Density of the polymer; Measured by ASTM D-792.

- Melt Index (MI) of the polymer was measured by ASTM D-1238 (Condition E, 230℃, 2.16 kg load).

Tensile strength, flexural strength and flexural modulus (Secant 1%): measured according to ASTM D790 using an INSTRON 3365 device.

Low-temperature and room-temperature impact strength: It was performed according to ASTM D256, and the impact strength was measured at room temperature (23 ℃) for the impact strength at room temperature (23 ℃) measured.

POE Comparative Example 1 Example 1 Comparative Example 2 Example 2 Melt Index (MI) 18.6 19.3 15.0 14.6 density 1.036 1.032 1.032 1.031 tensile strength 195 195 192 193 flexural strength 303 303 309 317 flexural modulus 17,637 17,676 19,189 19,296 Low temperature shock (@-30) 3.8 4.0 4.2 4.5 Room temperature shock (@ 23) 33.4 35.7 40.2 42.6

In Table 3, examples and comparative examples having the same or similar comonomer content, density, and melt index (MI) values were paired to compare their tensile strength. Referring to Table 3, it was confirmed that the polypropylene-based composites of Examples had improved physical properties, such as low-temperature impact strength and room-temperature impact strength, compared to the polypropylene-based composites of Comparative Examples having similar densities and melt index (MI) values.

Through this, when a polypropylene-based composite is prepared by using an olefin-based polymer satisfying the requirements of (1) to (4) together with polypropylene, the polypropylene-based composite is a polypropylene-based composite using another olefin-based polymer. It was confirmed that physical properties such as low temperature impact strength, room temperature impact strength, tensile strength, flexural strength, and flexural modulus were excellent at the same or similar level of density and flow index.

Claims (11)

(A) polypropylene, and
(B) a polypropylene-based composite comprising an olefin-based polymer satisfying the requirements of (1) to (4) below:
(1) Density (d): 0.85 g/cc to 0.89 g/cc;
(2) Melt Index (MI, 190° C., 2.16 kg load condition): 0.1 g/10 min to 15 g/10 min;
(3) molecular weight distribution (MWD): 1.0 to 3.0; and
(4) The number average molecular weight (Mn) and Z+1 average molecular weight (Mz+1) satisfy the following formula (1).
[Equation 1]
{Mn/(Mz+1)}×100 > 15
The method of claim 1,
The (A) polypropylene has a melt index of 0.5 g/10min to 100 g/10min measured at 230°C and a load of 2.16 kg, a polypropylene-based composite.
The method of claim 1,
The (A) polypropylene is an impact copolymer having a melt index of 0.5 g/10min to 100 g/10min measured at 230°C and a load of 2.16 kg, a polypropylene-based composite.
The method of claim 1,
The (B) olefin-based polymer further (5) density and melting temperature (Tm) satisfy the following formula (2), polypropylene-based composite material.
[Equation 2]
Tm = a×density- b (2350 < a < 2500, 1900 < b < 2100)
The method of claim 1,
The (B) olefin-based polymer further satisfies (6) hardness and melting temperature (Tm) of 1.0 < hardness / Tm < 1.3, a polypropylene-based composite.
The method of claim 1,
The (B) olefin-based polymer further satisfies (7) a weight average molecular weight (Mw): 10,000 to 500,000.
The method of claim 1,
The (B) olefin-based polymer further satisfies (8) Z+1 average molecular weight (Mz+1): 50,000 to 1,500,000.
The method of claim 1,
The (B) olefin-based polymer further satisfies (8) Z+1 average molecular weight (Mz+1): 80,000 g/mol to 1,000,000 g/mol.
The method of claim 1,
The polypropylene-based composite is a polypropylene-based composite comprising 5 to 40% by weight of the (B) olefin-based polymer.
The method of claim 1,
The polypropylene-based composite further comprises an inorganic filler, a polypropylene-based composite.
11. The method of claim 10,
The polypropylene-based composite includes the inorganic filler in an amount of 0.1 parts by weight to 40 parts by weight based on 100 parts by weight of polypropylene,
The inorganic filler has an average particle diameter (D ₅₀ ) of 1 μm to 20 μm, a polypropylene-based composite.