KR102444573B1 - Composition of metallocene polypropylene resin with high transparency - Google Patents

Abstract

The present invention relates to a metallocene polypropylene resin composition having excellent transparency, and more particularly, to a metallocene polypropylene resin composition having excellent transparency including a polypropylene resin prepared using a specific metallocene catalyst and a transparent nucleating agent in a specific combination. It relates to a polypropylene resin composition.

Description

Metallocene polypropylene resin composition with excellent transparency {COMPOSITION OF METALLOCENE POLYPROPYLENE RESIN WITH HIGH TRANSPARENCY}

The present invention relates to a metallocene polypropylene resin composition having excellent transparency, and more particularly, to a metallocene polypropylene resin composition having excellent transparency including a polypropylene resin prepared using a specific metallocene catalyst and a transparent nucleating agent in a specific combination. It relates to a polypropylene resin composition.

Propylene polymer has excellent moldability and mechanical strength and is inexpensive, so it is a general-purpose plastic that is used for a wide range of applications. In particular, in the injection field, many efforts have been made to improve properties such as rigidity, transparency, and high cycle injection moldability in injection molding without impairing various properties inherent in propylene polymers. It is known that these properties can be improved by increasing the crystallization temperature and rate of the propylene polymer and reducing the spheroid size. For this purpose, a method of increasing the crystallization temperature and crystallization rate of the propylene polymer by adding an external nucleating agent during the extrusion process after polymerization of propylene and reducing the size of spheroids is commercially used.

Representative nucleating agents include aluminum salts of aromatic carboxylic acids, dibenzylidene sorbitol and substituted dibenzylidene sorbitol. By prescribing these nucleating agents, the crystallization rate is increased in the process that polypropylene is solidified from a molten state to a solid state after cooling due to the presence of the nucleating agent. Shortening performance can be improved. However, since these nucleating agents, which were previously prescribed for polypropylene resins, are low molecular weight substances and require a large amount of prescription, they volatilize during product molding to contaminate odors and molds, or leached to the product surface after molding, causing surface defects and odor problems. can do it In addition, since the dispersibility in the propylene polymer is not good, efforts to increase the kneading property are required.

In addition, conventional attempts have been made to improve transparency by prescribing a mixture of sorbitol-based nucleating agents in polypropylene, but these nucleating agent mixtures are sufficiently dispersed in polypropylene to dramatically improve the transparency of the resin composition. did.

Korean Patent Laid-Open No. 10-2007-0017365 discloses a resin composition applied to polypropylene by synthesizing a transparent nucleating agent having various functional groups, but these nucleating agents are sufficiently dispersed in polypropylene to dramatically improve the transparency of the resin composition. There is a limit to not being able to show the effect.

The present invention has been devised to solve the above problems, and it is intended to provide a polypropylene resin composition with dramatically improved transparency by blending a specific combination of a sorbitol-based transparent nucleating agent with polypropylene prepared using a novel metallocene catalyst. .

화학식 1에서, M은 4족 전이금속이고; R1, R2, R3 및 R4은 각각 독립적으로 수소; 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₁-C₂₀)알킬기; 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₂-C₂₀)알케닐기; 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₁-C₂₀)알킬(C₆-C₂₀)아릴기; 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₆-C₂₀)아릴(C₁-C₂₀)알킬기; 또는 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₁-C₂₀)실릴기이고; R1, R2, R3 및 R4 중 2개 이상은 서로 연결되어 지방족 고리 또는 방향족 고리를 형성할 수 있고; R5, R6, R7 및 R8은 각각 독립적으로 수소; 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₁-C₂₀)알킬기; 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₂-C₂₀)알케닐기; 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₁-C₂₀)알킬(C₆-C₂₀)아릴기이고; R9, R10, R11, R12, R13, R14, R15 및 R16은 각각 독립적으로 수소; 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₁-C₂₀)알킬기; 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₂-C₂₀)알케닐기; 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₁-C₂₀)알킬(C₆-C₂₀)아릴기; 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₆-C₂₀)아릴(C₁-C₂₀)알킬기; 또는 아세탈기, 케탈기 또는 에테르기를 포함 또는 포함하지 않는 (C₁-C₂₀)실릴기이고; R9, R10, R11, R12, R13, R14, R15 및 R16 중 2개 이상은 서로 연결되어 지방족 고리 또는 방향족 고리를 형성할 수 있고; R17 및 R18은 각각 독립적으로 수소, (C₁-C₂₀)알킬기, (C₂-C₂₀)알케닐기, (C₂-C₂₀)알키닐기, (C₆-C₂₀)아릴기, (C₁-C₂₀)알킬(C₆-C₂₀)아릴기, (C₆-C₂₀)아릴(C₁-C₂₀)알킬기, (C₁-C₂₀)알킬아미드기 또는 (C₆-C₂₀)아릴아미드기이고; n은 정수 2이며,
[화학식 2]
-[Al(R19)-O]n-
화학식 2에서, R19는 할로겐 라디칼 또는 할로겐으로 치환 또는 비치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이고; n은 2 이상의 정수이며,
[화학식 3]
A(R20)₃
화학식 3에서, A는 알루미늄 또는 보론이고; R20은 서로 동일하거나 상이하고, 각각 독립적으로 할로겐 라디칼 또는 할로겐으로 치환 또는 비치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이며,
[화학식 4]
[L-H]⁺[Z(B)₄]^- 또는 [L]⁺[Z(B)₄]^-
화학식 4에서, L은 중성 또는 양이온성 루이스 산이고; H는 수소 원자이고; Z는 13족 원소이고; B는 각각 독립적으로 1 이상의 수소 원자가 할로겐 원소, 탄소수 1 내지 20의 하이드로카르빌기, 알콕시기, 또는 페녹시 라디칼로 치환된 탄소수 6 내지 20의 아릴 또는 알킬 라디칼이다.In order to solve the above problems, the present invention provides a transition metal compound represented by the following formula (1); and at least one cocatalyst compound selected from the group consisting of an aluminum compound represented by the following Chemical Formula 2, an alkyl metal compound represented by the following Chemical Formula 3, and a boron compound represented by the following Chemical Formula 4; Transition metal catalyst composition comprising a polypropylene; and a mixture of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3:2,4-bis(4-methylbenzylidene)sorbitol (MDBS); As a polypropylene resin composition, the haze (ASTM D1003) of a 1.25 mm thick specimen prepared using the polypropylene resin composition is 10% or less, and the polypropylene is a copolymer of propylene and an α-olefin having 2 to 10 carbon atoms. , α-olefin monomer in an amount of 1 to 5% by weight, and 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3:2,4-bis in the mixture The weight ratio of (4-methylbenzylidene)sorbitol (MDBS) is 1:9 to 9:1, and 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3 : A mixture of 2,4-bis(4-methylbenzylidene)sorbitol (MDBS) provides a polypropylene resin composition, characterized in that it is contained in an amount of 1,500 to 5,000 ppm with respect to the polypropylene.
[Formula 1]

In Formula 1, M is a Group 4 transition metal; R1, R2, R3 and R4 are each independently hydrogen; a (C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; a (C ₂ -C ₂₀ )alkenyl group with or without an acetal group, a ketal group, or an ether group; a (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group with or without an acetal group, a ketal group, or an ether group; a (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; or a (C ₁ -C ₂₀ )silyl group with or without an acetal group, a ketal group, or an ether group; at least two of R1, R2, R3 and R4 may be linked to each other to form an aliphatic ring or an aromatic ring; R5, R6, R7 and R8 are each independently hydrogen; a (C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; a (C ₂ -C ₂₀ )alkenyl group with or without an acetal group, a ketal group, or an ether group; a (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group with or without an acetal group, a ketal group, or an ether group; R9, R10, R11, R12, R13, R14, R15 and R16 are each independently hydrogen; a (C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; a (C ₂ -C ₂₀ )alkenyl group with or without an acetal group, a ketal group, or an ether group; a (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group with or without an acetal group, a ketal group, or an ether group; a (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; or a (C ₁ -C ₂₀ )silyl group with or without an acetal group, a ketal group, or an ether group; at least two of R9, R10, R11, R12, R13, R14, R15 and R16 may be linked to each other to form an aliphatic ring or an aromatic ring; R17 and R18 are each independently hydrogen, (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₂ -C ₂₀ )alkynyl group, (C ₆ -C ₂₀ )aryl group, (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkylamide group or (C ₆ -C ₂₀ ) ) an arylamide group; n is the integer 2,
[Formula 2]
-[Al(R19)-O]n-
In formula (2), R19 is a halogen radical or a hydrocarbyl radical having 1 to 20 carbon atoms substituted or unsubstituted with halogen; n is an integer greater than or equal to 2,
[Formula 3]
A(R20) ₃
In formula (3), A is aluminum or boron; R20 is the same as or different from each other, and each independently represents a halogen radical or a hydrocarbyl radical having 1 to 20 carbon atoms substituted or unsubstituted with halogen,
[Formula 4]
[LH] ⁺ [Z(B) ₄ ] ^- or [L] ⁺ [Z(B) ₄ ] ^-
In formula (4), L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a group 13 element; B is each independently an aryl or alkyl radical having 6 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a halogen element, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group, or a phenoxy radical.

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In the present invention, at least one of R1, R2, R3 and R4 is hydrogen, and the rest are each independently (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₆ -C ₂₀ ) may be a (C ₁ -C ₂₀ )silyl group with or without an aryl group or an acetal group, a ketal group, or an ether group; R1, R2, R3 and R4 At least two of them are linked to each other to provide a polypropylene resin composition, characterized in that it can form an aliphatic ring or an aromatic ring.

The present invention also provides a polypropylene resin composition, characterized in that at least one of R1, R2, R3 and R4 is hydrogen, and the rest are independently (C ₁ -C ₂₀ )alkyl groups.

In the present invention, at least two or more of R1, R2, R3 and R4 are hydrogen, and the rest are each independently (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₆ -C ₂₀ ) may be a (C ₁ -C ₂₀ )silyl group with or without an aryl group or an acetal group, a ketal group, or an ether group; Two of R1, R2, R3 and R4 are connected to each other to provide a polypropylene resin composition, characterized in that it can form an aliphatic ring or an aromatic ring.

The present invention also provides a polypropylene resin composition, characterized in that at least two or more of R1, R2, R3 and R4 are hydrogen, and the rest are independently (C ₁ -C ₂₀ )alkyl groups.

In the present invention, the aluminum compound cocatalyst is one or a mixture of two or more selected from alkylaluminoxane or organoaluminum, methylaluminoxane, tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum, trioctyl It is a single or a mixture of two or more selected from aluminum, and the boron compound promoter is tris(pentafluorophenyl)borane, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and triphenylmethylinium tetrakis It provides a polypropylene resin composition, characterized in that it is selected from (pentafluorophenyl) borate alone or a mixture thereof.

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The polypropylene resin composition according to the present invention includes a polypropylene resin prepared using a specific metallocene catalyst and a specific transparent nucleating agent mixture, so that transparency can be significantly improved.

Hereinafter, preferred embodiments of the present invention will be described in detail. In describing the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted. Throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

The present invention relates to a transition metal compound represented by the following formula (1); and at least one cocatalyst compound selected from the group consisting of an aluminum compound represented by the following Chemical Formula 2, an alkyl metal compound represented by the following Chemical Formula 3, and a boron compound represented by the following Chemical Formula 4; Transition metal catalyst composition comprising a polypropylene copolymer; and a mixture of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3:2,4-bis(4-methylbenzylidene)sorbitol (MDBS); As a polypropylene resin composition, a haze (ASTM D1003) of a 1.25 mm thick specimen prepared using the polypropylene resin composition is 10% or less.

[Formula 1]

In Formula 1,

M is a Group 4 transition metal;

R1, R2, R3 and R4 are each independently hydrogen; a (C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; a (C ₂ -C ₂₀ )alkenyl group with or without an acetal group, a ketal group, or an ether group; a (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group with or without an acetal group, a ketal group, or an ether group; a (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; or a (C ₁ -C ₂₀ )silyl group with or without an acetal group, a ketal group, or an ether group; two of R1, R2, R3 and R4 may be linked to each other to form an aliphatic ring or an aromatic ring;

R5, R6, R7 and R8 are each independently hydrogen; a (C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; a (C ₂ -C ₂₀ )alkenyl group with or without an acetal group, a ketal group, or an ether group; a (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group with or without an acetal group, a ketal group, or an ether group;

R9, R10, R11, R12, R13, R14, R15 and R16 are each independently hydrogen; a (C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; a (C ₂ -C ₂₀ )alkenyl group with or without an acetal group, a ketal group, or an ether group; a (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group with or without an acetal group, a ketal group, or an ether group; a (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; or a (C ₁ -C ₂₀ )silyl group with or without an acetal group, a ketal group, or an ether group; at least two of R9, R10, R11, R12, R13, R14, R15 and R16 may be linked to each other to form an aliphatic ring or an aromatic ring;

R17 and R18 are each independently hydrogen, (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₂ -C ₂₀ )alkynyl group, (C ₆ -C ₂₀ )aryl group, (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkylamide group or (C ₆ -C ₂₀ ) ) an arylamide group;

n is the integer 2,

[Formula 2]

-[Al(R19)-O]n-

In formula (2), R19 is a halogen radical or a hydrocarbyl radical having 1 to 20 carbon atoms substituted or unsubstituted with halogen; n is an integer greater than or equal to 2,

[Formula 3]

A(R20) ₃

In formula (3), A is aluminum or boron; R20 is the same as or different from each other, and each independently represents a halogen radical or a hydrocarbyl radical having 1 to 20 carbon atoms substituted or unsubstituted with halogen,

[Formula 4]

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

In formula (4), L is a neutral or cationic Lewis acid; H is a hydrogen atom;

Z is a group 13 element; B is each independently an aryl or alkyl radical having 6 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a halogen element, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group, or a phenoxy radical.

As used herein, the term “alkyl” refers to a monovalent straight-chain or branched saturated hydrocarbon radical composed of only carbon and hydrogen atoms, and examples of such alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- butyl, pentyl, hexyl, octyl, dodecyl, and the like.

Also, as used herein, the term "cycloalkyl" refers to a monovalent alicyclic alkyl radical composed of a single ring, and examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like.

Also, as used herein, the term "alkenyl" refers to a straight-chain or branched hydrocarbon radical containing at least one carbon-carbon double bond, and includes ethenyl, propenyl, butenyl, pentenyl, etc., but not limited

In addition, the term "aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

Also, as used herein, the term “alkoxy” refers to an —O-alkyl radical, where “alkyl” is as defined above. Examples of such alkoxy radicals include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, and the like.

In addition, the term "halogen" described in the present invention means a fluorine, chlorine, bromine or iodine atom.

In the present invention, the transition metal compound is an ansa containing a cyclopentadiene derivative ligand connected to each other by a bridging group of silicone or alkenylene and an indenyl derivative ligand in which an aryl is necessarily substituted at the 4th position, as shown in Formula 1 -It has an ansa-metallocene structure.

As such, the transition metal compound has an indene derivative ligand substituted with an aryl at the 4-position, and thus has superior catalytic activity and copolymerizability compared to the transition metal compound having an unsubstituted ligand with an aryl group at the 4-position of the indene. .

Here, in the transition metal compound according to the present invention, at least one, preferably two or more, of R1, R2, R3 and R4 in the structure of Formula 1 is hydrogen, and the rest are each independently (C ₁ -C ₂₀ )alkyl groups. , (C ₂ -C ₂₀ )alkenyl group, (C ₆ -C ₂₀ )aryl group or (C ₁ -C ₂₀ )silyl group with or without an acetal group, ketal group, or ether group; At least two of R1, R2, R3 and R4 are preferably linked to each other to form an aliphatic ring or an aromatic ring, more preferably at least one or more of R1, R2, R3 and R4, preferably In particular, when two or more are hydrogen and the rest are independently substituted with (C ₁ -C ₂₀ )alkyl groups, polypropylene has excellent activity and high molecular weight polypropylene can be produced during polymerization of polypropylene.

On the other hand, the transition metal compound of Formula 1 is an active catalyst component used for propylene polymerization, by extracting the ligand in the transition metal compound to cationize the central metal while acting as a counterion having weak binding force, that is, an anion. The compounds represented by 2 to 4 act together as a co-catalyst.

In order for the promoter compound to exhibit a more excellent activation effect, the compound represented by Formula 2 is not particularly limited as long as it is an alkylaluminoxane, but preferred examples include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butyl aluminoxane and the like, and a particularly preferred compound is methylaluminoxane.

In addition, the alkyl metal compound represented by Formula 3 is not particularly limited, but preferred examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxy seed, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, and particularly preferred compounds may be selected from trimethylaluminum, triethylaluminum and triisobutylaluminum. have.

In addition, in the promoter compound represented by Formula 4, the [LH] ⁺ is a dimethylanilinium cation, the [Z(A) ₄ ] ^- is [B(C6F5) ₄ ] ^- Preferably, the [ L] ⁺ is [(C ₆ H ₅ ) 3C] ⁺ , and [Z(A) ₄ ] ^- is preferably [B(C ₆ F ₅ ) ₄ ] ^- . Here, the promoter compound represented by Formula 4 is not particularly limited, but non-limiting examples include triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, and tripropylammonium tetraphenyl. Borate, trimethylammonium tetra(p-tolyl) borate, tripropylammonium tetra(p-tolyl) borate, trimethylammonium tetra(o,p-dimethylphenyl) borate, triethylammonium tetra(o,p-dimethyl Phenyl) borate, tributylammonium tetra(p-trifluoromethylphenyl) borate, trimethylammonium tetra(p-trifluoromethylphenyl) borate, tributylammonium tetrapentafluorophenyl borate, N,N-diethyl Amilidium tetrapetyl borate, N,N-diethylanilideium tetraphenylborate, N,N-diethylaniliniumtetrapentafluorophenylborate, diethylammoniumtetrapentafluorophenylborate, triphenylphos Phoniumtetraphenylborate, trimethylphosphoniumtetraphenylborate, triphenylcarboniumtetra(p-trifluoromethylphenyl)borate, triphenylcarboniumtetrapentafluorophenylborate, dimethylaniliniumtetrakis(pentafluoro phenyl) borate.

After preparing a catalyst composition using the compounds of Chemical Formulas 1 to 4, it can be used for olefin polymerization, but a method for preparing the catalyst composition is not particularly limited.

The addition amount of the promoter compound may be determined in consideration of the addition amount of the transition metal compound represented by Formula 1 and the amount required to sufficiently activate the promoter compound. The content of the promoter compound may be 1:1 to 100,000 based on the molar ratio of the metal contained in the promoter compound to 1 mole of the transition metal contained in the transition metal compound represented by Formula 1, preferably 1:1 to 10,000, more preferably 1:1 to 5,000.

More specifically, in the first method, the compound represented by Formula 2 is preferably in a molar ratio of 1:10 to 5,000, more preferably in a molar ratio of 1:50 to 1,000, with respect to the transition metal compound represented by Formula 1, most Preferably, it may be included in a molar ratio of 1:100 to 1,000. When the molar ratio of the compound represented by Formula 2 to the transition metal compound of Formula 1 is less than 1:10, the amount of aluminoxane is very small, so that the activation of the metal compound cannot completely proceed, and 1:5,000 In the case of exceeding this, an excess of aluminoxane may act as a catalyst poison and may play a role in preventing the polymer chain from growing well.

In addition, as a second method, when A is boron in the promoter compound represented by Formula 3, 1:1 to 100, preferably 1:1 to 10, more with respect to the transition metal compound represented by Formula 1 Preferably, it may be supported in a molar ratio of 1:1 to 3. In addition, when A is aluminum in the promoter compound represented by Formula 3, it may vary depending on the amount of water in the polymerization system, but 1:1 to 1000, preferably 1 to the transition metal compound represented by Formula 1 It may be supported in a molar ratio of :1 to 500, more preferably 1:1 to 100.

In addition, the promoter compound represented by the formula (4) is supported in a molar ratio of 1:0.5-30, preferably 1:0.7-20, more preferably 1:1-10 with respect to the transition metal compound represented by the formula (1). can be When the ratio of the cocatalyst compound represented by Formula 4 is less than 1:0.5, the amount of the activator is relatively small, so that the metal compound cannot be completely activated, so there may be a problem in that the activity of the resulting catalyst composition decreases, 1 If it exceeds: 30, the metal compound is fully activated, but there may be a problem in that the unit price of the catalyst composition is not economical or the purity of the resulting polymer is lowered with the remaining excess activator.

Meanwhile, in the present invention, the catalyst may further include a carrier in the compound represented by Formula 1 and the cocatalyst compound.

As the carrier, a carrier of an inorganic or organic material used in the preparation of a catalyst in the art to which the present invention belongs may be used without limitation, for example, SiO ₂ , Al ₂ O ₃ , MgO, MgCl ₂ , CaCl ₂ , ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , SiO ₂ -Al ₂ O ₃ , SiO ₂ -MgO, SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -CrO ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, bauxite, zeolite, starch, cyclodextrin, synthetic polymer, etc. may be used. Preferably, the carrier includes a hydroxyl group on the surface, and may be at least one carrier selected from the group consisting of silica, silica-alumina, and silica-magnesia.

The method of supporting the transition metal compound and the promoter compound on the carrier is a method of directly supporting the transition metal compound on a dehydrated carrier, the carrier is pretreated with the promoter compound, and then the transition metal compound is A supporting method, a method in which the transition metal compound is supported on the carrier and post-treatment with a promoter compound, a method in which the transition metal compound and the promoter compound are reacted and then a carrier is added to react, etc. may be used.

The solvent usable in the supporting method may be an aromatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated aliphatic hydrocarbon-based solvent, or a mixture thereof. Here, the aliphatic hydrocarbon-based solvent is a non-limiting example, pentane (Pentane), hexane (Hexane), heptane (Heptane), octane (Octane), nonane (Nonane), decane (Decane), undecane (Undecane), dode Dodecane, etc. are mentioned. In addition, non-limiting examples of the aromatic hydrocarbon-based solvent include benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, and the like. In addition, the halogenated aliphatic hydrocarbon-based solvent includes, but is not limited to, dichloromethane, trichloromethane, dichloroethane, trichloroethane, and the like.

In addition, the process of supporting the transition metal compound and the cocatalyst compound on the carrier is advantageous in terms of efficiency of the supporting process to be carried out at a temperature of -70 to 200, preferably -50 to 150, more preferably 0 to 100. do.

The catalyst prepared according to the above preparation method has high catalytic activity, and since polypropylene polymerized using the catalyst has a high molecular weight and a low melt index, physical properties can also be improved.

According to an embodiment of the present invention, a polymer produced through a polymerization process carried out by direct contact of propylene and an α-olefin monomer compound has a relatively insoluble and/or immobilized catalytic site such that the polymer chain is rapidly immobilized according to this information. It can be prepared by polymerizing propylene and α-olefin monomers under the following conditions. Such immobilization can be effected, for example, by using a solid insoluble catalyst, carrying out the polymerization in a medium in which the resulting polymer is generally insoluble, and maintaining the polymerization reactants and products below the crystalline melting point of the polymer.

In the present invention, the polypropylene is a propylene homopolymer or a copolymer obtained by polymerizing propylene and an α-olefin having 2 to 10 carbon atoms, preferably a copolymer of propylene and ethylene, and most preferably a propylene and ethylene random copolymer. may be synthetic.

In the present invention, the polypropylene may contain 1 to 5% by weight of the α-olefin monomer, preferably 1 to 4% by weight, more preferably 2 to 4% by weight, most preferably 3 to 4% by weight % can be included. When the content of the α-olefin monomer in the polypropylene is less than 1% by weight, transparency improvement may be insufficient, and when it exceeds 5% by weight, mechanical properties of the polypropylene may be deteriorated.

Polymerization processes suitable for polymerization of the polypropylene in the present invention are well known to those skilled in the art, and include bulk polymerization, solution polymerization, slurry polymerization and low pressure gas phase polymerization. The metallocene catalyst compositions are particularly useful in known types of operation using fixed bed, moving bed or slurry processes conducted in single, series or parallel reactors.

When the polymerization reaction is carried out in a liquid phase or a slurry phase, a solvent, propylene, or an olefinic monomer itself may be used as a medium.

Since the catalyst composition presented in the present invention exists in a uniform form in the polymerization reactor, it is preferable to apply it to a solution polymerization process carried out at a temperature higher than the melting point of the polymer. However, as disclosed in U.S. Patent No. 4,752,597, the heterogeneous catalyst composition obtained by supporting the transition metal catalyst and cocatalyst on a porous metal oxide support may be used in slurry polymerization or gas phase polymerization process. Therefore, when the catalyst composition of the present invention is used together with an inorganic carrier or an organic polymer carrier, it can be applied to a slurry or gas phase process. That is, the transition metal compound and the cocatalyst compound may be used in a form supported on an inorganic carrier or an organic polymer carrier.

The solvent that can be used in the polymerization reaction may be an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated aliphatic hydrocarbon-based solvent, or a mixture thereof. Here, the aliphatic hydrocarbon-based solvent is a non-limiting example, butane (Butane), isobutane (Isobutane), pentane (Pentane), hexane (Hexane), heptane (Heptane), octane (Octane), nonane (Nonane), decane (Nonane), (Decane), undecane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, and the like. In addition, the aromatic hydrocarbon-based solvent is a non-limiting example, benzene (Benzene), monochlorobenzene (Monochlorobenzene), dichlorobenzene (Dichlorobenzene), trichlorobenzene (Trichlorobenzene), toluene (Toluene), xylene (Xylene), chlorobenzene (Chlorobenzene) and the like. In addition, the halogenated aliphatic hydrocarbon solvent is a non-limiting example, dichloromethane (Dichloromethane), trichloromethane (Trichloromethane), chloroethane (Chloroethane), dichloroethane (Dichloroethane), trichloroethane (Trichloroethane), 1,2-dichloroethane (1,2-Dichloroethane) and the like.

In the present invention, the polypropylene may be prepared by polymerizing propylene and an α-olefin-based monomer compound in the presence of the transition metal catalyst composition. At this time, the transition metal catalyst and the cocatalyst component may be separately introduced into the reactor or each component may be mixed in advance and put into the reactor, and mixing conditions such as the order of introduction, temperature or concentration are not separately limited.

On the other hand, in the present invention, the amount of the catalyst added in the process of polymerizing the polypropylene may be determined within a range in which the polymerization reaction of the monomers can sufficiently occur according to the slurry phase, liquid phase, gas phase, or bulk phase, and thus is not particularly limited. However, the amount of the catalyst added is preferably 10 ^-8 to 1 mol/L based on the concentration of the central metal (M) in the main catalyst compound (transition metal compound) per unit volume (L) of the monomer, and 10 ^-7 It is more preferably from 10 ^-1 mol/L, and even more preferably from 10 ^-7 to 10 ^-2 mol/L.

In this case, in the step of polymerizing the propylene and the α-olefin monomer, hydrogen may be added, and the amount of hydrogen to be added may control the chain length of the polypropylene. That is, when the amount of hydrogen to be input is large, a polypropylene copolymer having a low molecular weight may be prepared, and when the amount of hydrogen to be input is small, a polypropylene copolymer having a large molecular weight may be manufactured. A preferred dosage of hydrogen to play this role may be 0.1 to 50 mg, preferably 1 to 30 mg, more preferably 5 to 20 mg, and most preferably 10 to 15 mg.

In addition, in the present invention, the polymerization reaction is made of a batch type, semi-continuous type, or continuous type reaction, and preferably, a continuous type reaction.

In the present invention, the temperature and pressure conditions of the polymerization reaction may be determined in consideration of the efficiency of the polymerization reaction depending on the type of reaction and the type of reactor to be applied, but the polymerization temperature may be 40 to 150, preferably 60 to 100. and the pressure may be 1 to 100 atmospheres, preferably 5 to 50 atmospheres.

In the present invention, the polypropylene prepared using the specific metallocene catalyst may exhibit a high molecular weight and a low melt index by using a catalyst including a main catalyst compound and a cocatalyst compound.

On the other hand, in the polypropylene resin composition of the present invention, 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1, By blending a mixture of 3:2,4-bis(4-methylbenzylidene)sorbitol (MDBS), the transparency of the final resin composition can be dramatically improved.

Conventionally, a mixture of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3:2,4-bis(4-methylbenzylidene)sorbitol (MDBS) was mixed with polypropylene resin. Attempts were made to improve the transparency of the composition by blending with the mixture, but the transparent nucleating agent mixture was not sufficiently dispersed in the polypropylene resin, so there was a limit to improving the transparency. In contrast, in the present invention, a polypropylene copolymer prepared using the specific metallocene catalyst and prepared using another metallocene catalyst by mixing the transparent nucleating agent mixture with a polypropylene copolymer having a specific α-olefin content It is possible to provide a polypropylene resin composition that exhibits significantly improved transparency compared to a composition comprising a coalescence.

In the present invention, the mixture of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3:2,4-bis(4-methylbenzylidene)sorbitol (MDBS) is It may be included at 1,500 to 5,000 ppm with respect to the polypropylene copolymer, preferably from 1,500 to 4,500 ppm, and most preferably from 2,000 to 4,000 ppm. When the content of the transparent nucleating agent mixture in the composition is less than 1,500 ppm, the improvement of transparency may be insufficient.

In the present invention, the weight ratio of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3:2,4-bis(4-methylbenzylidene)sorbitol (MDBS) is 1:9 to 9:1, preferably 2:8 to 8:2, more preferably 3:7 to 7:3, most preferably 4:6 to 6: can be 4

In the present invention, the polypropylene copolymer and 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3:2,4-bis(4-methylbenzylidene)sorbitol ( MDBS) may be mixed in a reactor such as an extruder and then melt-kneaded to form a specimen.

The polypropylene resin composition of the present invention may further include one or more conventional additives known in the art as other additives other than the above components, such as a slip agent, an anti-blocking agent, an antioxidant, a neutralizing agent, a UV stabilizer, an antistatic agent, and the like. can At this time, each additive may be included in the range of 0.01 to 1 part by weight based on 100 parts by weight of the resin composition of the present invention.

The polypropylene resin composition of the present invention may have a haze (ASTM D1003) of 10% or less, preferably 9% or less, and most preferably 7% or less of a 1.25 mm thick specimen prepared using the same.

A specific embodiment according to the present invention will be described.

Except where otherwise noted, all ligand and catalyst synthesis experiments were performed using standard Schlenk or glovebox technology under a nitrogen atmosphere, and the organic solvents used for all reactions were refluxed under sodium metal and benzophenone for moisture. was removed and used by distillation immediately before use. 1 ^H -NMR analysis of the synthesized ligand and catalyst was performed at room temperature using a Bruker 300 MHz.

Toluene, a polymerization solvent, was used after passing through a tube filled with molecular sieve 5A and activated alumina and bubbling with high-purity nitrogen to sufficiently remove moisture, oxygen and other catalyst poisons. All polymerizations were carried out in a high-pressure reactor (autoclave) completely blocked from outside air, after injecting the required amount of solvent, co-catalyst, and each monomer to be polymerized, and then adding the catalyst.

[Catalyst Preparation Example]

Transition metal compound (tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4- (4-t-butylphenyl ) Synthesis of indenyl zirconium ditetrahydroborate (Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-tert-butylphenyl)indenyl Zr ditetrahydrobrate)

1) Synthesis of dimethyl tetramethylcyclopentadienyl chlorosilane

Put tetrahydrofuran (600ml) and tetramethylcyclopentadiene (50g) in a 2l flask, and slowly add n-BuLi (2.5M hexane solution) (170ml) dropwise at -10 under a nitrogen atmosphere, and then at room temperature for 12 hours. The reaction was stirred for a while. After lowering the temperature of the reaction solution to -10 again, dimethyl dichlorosilane (170 g) was added thereto, followed by stirring at room temperature for 12 hours to react, and then the reaction product was vacuum dried. Here, n-hexane (500 mL) was added to dissolve the reaction product, filtered through a Celite filter, and the filtered solution was vacuum dried to obtain 70 g of dimethyl tetramethylcyclopentadienylchlorosilane in the form of yellow oil (yield: 80%).

2) Synthesis of dimethyl tetramethylcyclopentadienyl 2-methyl-4-(4-t-butylphenyl)indenyl silane (Dimethyl tetramethylcyclopentadienyl 2-methyl-4-(4-tert-butylphenyl)indenyl silane)

Toluene (200 mL), tetrahydrofuran (40 mL), and 2-methyl-4- (4-t-butylphenyl) indene (50 g) were added to the flask was cooled to -10, and then n-BuLi (2.5 M) hexane solution) (76 mL) was slowly added dropwise, followed by stirring at room temperature for 12 hours. After lowering the temperature of the reactant to -10 again, dimethyl tetramethylcyclopentadienylchlorosilane (38 g) was added thereto, and the reaction was stirred at room temperature for 12 hours. Upon completion of the reaction, water (400 ml) was added, and the mixture was stirred at room temperature for 1.5 hours, extracted with toluene, and dried under vacuum to form a yellow oil dimethyl tetramethylcyclopentadienyl 2-methyl-4-(4-t). -Butylphenyl)indenylsilane 80g was obtained (yield 95%).

3) Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyl zirconium dichloride (Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4- (4-tert-butylphenyl) indenyl Zr dichloride) synthesis

Dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenyl silane (50 g), toluene (300 mL) and diethyl ether (100 mL) were placed in a flask and cooled to -10. Next, n-BuLi (2.5M hexane solution) (90 mL) was slowly added dropwise. After the dropwise addition was completed, the reaction temperature was raised to room temperature, stirred for 48 hours, and then filtered. The obtained filtrate was vacuum dried to obtain 40 g (yield 80%) of tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-t-butylphenyl)indenyl dilithium salt in the form of a solid, which was not purified. and was immediately used in the next reaction.

Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-t-butylphenyl)indenyl dilithium salt (40 g), toluene (40 mL) and ether (10 mL) were placed in flask #1 and stirred . A mixture of toluene (30 mL) and ZrCl ₄ (20 g) was prepared in flask #2. The mixed solution of flask #2 was slowly added dropwise to flask #1 using a cannula, followed by stirring at room temperature for 24 hours. After stirring, the mixture was vacuum-dried, extracted with methylene chloride (500 mL), filtered through a Celite filter, and the filtrate was vacuum-dried. The obtained solid was washed with a 1:3 mixture of methylene chloride and n-hexane (50 ml), and then dried under vacuum to form a yellow solid tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-t). -Butylphenyl) indenyl zirconium dichloride 32g was obtained (yield 60%).

4) Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-t-butylphenyl)indenyl zirconium ditetrahydroborate (Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-tert-butylphenyl)indenyl Zr ditetrahydrobrate ) synthesis

Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyl zirconium dichloride (5.2 g), sodium tetraborate (1.5 g), tetrahydrofuran (100 ml) were added to a flask and reacted at room temperature for 12 hours. Then, the solid part was filtered, and the obtained solution part was vacuum-dried to obtain a white solid. The obtained white solid was transferred to a flask containing 500 ml of diethyl ether and stirred at room temperature for 5 hours. Then, the insoluble portion was removed using a filter, and diethyl ether was blown under vacuum to obtain 3.3 g of tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-t-butylphenyl)indenyl zirconium ditetrahydroborate. .

Supported Catalyst Preparation Example 1

Silica (manufacturer: Grace, product name: XPO-2412, 2.0 g) was placed in a Schlenk flask (100 ml) in a glove box, and 10 ml of anhydrous toluene solution was added thereto. Herein, about 10.2 ml of methylaluminoxane (10 wt% solution of methylaluminoxane in toluene, 15 mmol based on Al, manufacturer: Albemarle) was slowly added dropwise at 10 and stirred at 0 for about 1 hour, and then the temperature was raised to 70. Stir for 3 h and cool to 25 °C. Separately, in a glove box, the synthesized tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-t-butylphenyl)indenyl zirconium ditetrahydroborate (0.056 g, 100 μmol) was mixed with another 100 It was placed in a ml Schlenk flask, taken out of the glove box, and then 10 ml of anhydrous toluene solution was added. Here, the solution containing the transition metal compound in step 10 was slowly added to a solution containing silica and methylaluminoxane, and then the temperature was raised to 70 and stirred for 1 hour, then cooled to 25 and stirred for about 24 hours. . Thereafter, the obtained reaction product was washed with sufficient amounts of toluene and hexane to remove unreacted aluminum compounds. Then, it was dried in vacuo to obtain 2.70 g of a free-flowing supported catalyst.

Supported Catalyst Preparation Example 2

In Preparation Example 1 of the supported catalyst, tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4-(4-t-butylphenyl)indenyl zirconium ditetrahydroborate instead of tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4 -(4-t-Butylphenyl)indenyl zirconium dichloride was used, and the same procedure as in Preparation Example 1 of the supported catalyst was carried out.

[Example 1]

The inside of a stainless steel autoclave having an internal capacity of 2L at room temperature was completely replaced with nitrogen. While maintaining nitrogen purging, 2 ml of triisobutylaluminum (1M solution in hexane) and 500 g of propylene and 25 g of ethylene were injected into the reactor, and then 50 mg of the supported catalyst prepared in Preparation Example 1 of the supported catalyst was added to 5 ml of hexane. was dispersed and added to the reactor using high-pressure nitrogen. Then, polymerization was carried out at 70 to 60 minutes. After polymerization was completed, the reactor was cooled to room temperature, and excess propylene was removed through a discharge line to obtain a white powdery solid. The obtained white solid powder was dried over 15 hours while heating to 80 using a vacuum oven to prepare a polypropylene resin having an ethylene content of 1.5 wt%.

The 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3:2,4-bis(4-methylbenzylidene)sorbitol (MDBS) were mixed in a weight ratio of 8:2. After mixing 2,000 ppm of the mixed mixture with the polypropylene resin prepared above, it was melt-kneaded in a temperature range of about 195 to 230 by a single screw extruder. Then, a specimen of the target polypropylene was produced by a Dongshin hydraulic 150-ton injection molding machine. The molding machine barrel was set at a temperature of 220. The thickness of the specimen was 1.25 mm, and the specimen was aged at room temperature for 24 hours to obtain a final specimen.

[Example 2]

A specimen was prepared in the same manner as in Example 1, except that in Example 1, a mixture having a weight ratio of DMDBS to MDBS of 7:3 was used.

[Example 3]

A specimen was prepared in the same manner as in Example 1, except that a mixture of DMDBS and MDBS in a weight ratio of 5:5 was used in Example 1.

[Comparative Example 1]

A specimen was prepared in the same manner as in Example 1, except that in Example 1, a mixture having a weight ratio of DMDBS and MDBS of 10:0 was used.

[Comparative Example 2]

A specimen was prepared in the same manner as in Example 1, except that in Example 1, a mixture having a weight ratio of DMDBS and MDBS of 0:10 was used.

[Comparative Example 3]

A specimen was prepared in the same manner as in Example 1, except that DMDBS and MDBS were not included in the composition in Example 1.

After evaluating the haze of the specimens prepared in Examples and Comparative Examples according to ASTM D1003, the results are shown in Table 1 below.

[Table 1]

Referring to Table 1, it can be seen that the polypropylene resin compositions (Examples 1 to 3) including a mixture of DMDBS and MDBS have very good transparency. At this time, it was found that the closer the ratio of DMDBS to MDBS to 5:5, the greater the improvement in transparency.

On the other hand, when only one material of DMDBS and MDBS was mixed with the polypropylene resin (Comparative Examples 1 and 2), it was confirmed that the improvement in transparency was not large compared to the Example.

Additional Examples and Comparative Examples

Polypropylene (homopolymer or ethylene-propylene copolymer), DMDBS and MDBS were mixed according to the combinations shown in Table 2 below and then melt-kneaded by a single screw extruder at a temperature in the range of about 195 to 230. Then, a specimen of the target polypropylene was produced by a Dongshin hydraulic 150-ton injection molding machine. The molding machine barrel was set at a temperature of 220. The thickness of the specimen was 1.25 mm, and the specimen was aged at room temperature for 24 hours to obtain a final specimen.

After evaluating the haze (%) of the specimens prepared in Examples and Comparative Examples according to ASTM D1003, the results are shown in Table 2 below.

[Table 2]

In Table 2 above,

(1) "H-PP" is a homo polypropylene prepared using the supported catalyst prepared in Preparation Example 1 of the supported catalyst,

(2) "R-PP (EL 1.2%)" is an ethylene-propylene random copolymer having an ethylene content of 1.2% by weight prepared using the supported catalyst prepared in Preparation Example 1 of the supported catalyst,

(3) "R-PP (EL 3.7%)" is an ethylene-propylene random copolymer having an ethylene content of 3.7% by weight prepared using the supported catalyst prepared in Preparation Example 1 of the supported catalyst,

(4) The "mixed" refers to a mixture in which DMDBS and MDBS are mixed in a 1:1 ratio,

(5) The above mixing, DMDBS and MDBS values in parentheses indicate the concentration of each transparent nucleating agent with respect to the polypropylene resin in ppm.

However, in Comparative Example 12, a polypropylene resin prepared using the supported catalyst prepared in Preparation Example 2 of the supported catalyst was used.

Referring to Table 2, when the polypropylene resin prepared using a specific metallocene catalyst contains a transparent nucleating agent mixture in which DMDBS and MDBS are mixed 1:1 in a specific content (Examples 4 and 5), the preparation It was confirmed that the haze value of the prepared specimen was significantly lowered and the transparency was very good.

On the other hand, when no transparent nucleating agent was added to the same polypropylene resin as in Example (Comparative Example 4), it can be seen that the transparency is very low, and even if a mixture in which DMDBS and MDBS are mixed in 1:1 is mixed, When the content was too low (Comparative Example 5), it was confirmed that there was a limit to the improvement of transparency. In addition, when DMDBS or MDBS was included alone (Comparative Examples 6 to 11), it was confirmed that even if the amount of the transparent nucleating agent increased, there was a limit to the improvement of transparency.

On the other hand, when a polypropylene resin prepared using a metallocene catalyst composition other than the specific metallocene catalyst composition of the present invention is included (Comparative Example 12), transparency is improved even when the transparent nucleating agent mixture is included in a high concentration It can be seen that there is a limit to

A preferred embodiment of the present invention has been described in detail above. The description of the present invention is for illustration, and those skilled in the art to which the present invention pertains will understand that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention.

Accordingly, the scope of the present invention is indicated by the claims described below rather than the above detailed description, and all changes or modifications derived from the meaning, scope, and equivalent concept of the claims are included in the scope of the present invention. should be interpreted

Claims (10)

a transition metal compound represented by the following formula (1); and at least one cocatalyst compound selected from the group consisting of an aluminum compound represented by the following Chemical Formula 2, an alkyl metal compound represented by the following Chemical Formula 3, and a boron compound represented by the following Chemical Formula 4; Transition metal catalyst composition comprising a polypropylene; and
Poly containing; mixture of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3:2,4-bis(4-methylbenzylidene)sorbitol (MDBS); A propylene resin composition comprising:
The haze (ASTM D1003) of the 1.25 mm thick specimen prepared using the polypropylene resin composition is 10% or less,
The polypropylene is a copolymer of propylene and an α-olefin having 2 to 10 carbon atoms, and contains 1 to 5% by weight of an α-olefin monomer,
In the mixture, the weight ratio of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3:2,4-bis(4-methylbenzylidene)sorbitol (MDBS) is 1 :9 to 9:1;
The mixture of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) and 1,3:2,4-bis(4-methylbenzylidene)sorbitol (MDBS) is the polypropylene Polypropylene resin composition, characterized in that it is included in 1,500 ~ 5,000ppm with respect to:
[Formula 1]

In Formula 1,
M is a Group 4 transition metal;
R1, R2, R3 and R4 are each independently hydrogen; a (C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; a (C ₂ -C ₂₀ )alkenyl group with or without an acetal group, a ketal group, or an ether group; a (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group with or without an acetal group, a ketal group, or an ether group; a (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; or a (C ₁ -C ₂₀ )silyl group with or without an acetal group, a ketal group, or an ether group; at least two of R1, R2, R3 and R4 may be linked to each other to form an aliphatic ring or an aromatic ring;
R5, R6, R7 and R8 are each independently hydrogen; a (C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; a (C ₂ -C ₂₀ )alkenyl group with or without an acetal group, a ketal group, or an ether group; a (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group with or without an acetal group, a ketal group, or an ether group;
R9, R10, R11, R12, R13, R14, R15 and R16 are each independently hydrogen; a (C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; a (C ₂ -C ₂₀ )alkenyl group with or without an acetal group, a ketal group, or an ether group; a (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group with or without an acetal group, a ketal group, or an ether group; a (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group with or without an acetal group, a ketal group, or an ether group; or a (C ₁ -C ₂₀ )silyl group with or without an acetal group, a ketal group, or an ether group; at least two of R9, R10, R11, R12, R13, R14, R15 and R16 may be linked to each other to form an aliphatic ring or an aromatic ring;
R17 and R18 are each independently hydrogen, (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₂ -C ₂₀ )alkynyl group, (C ₆ -C ₂₀ )aryl group, (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkylamide group or (C ₆ -C ₂₀ ) ) an arylamide group;
n is the integer 2,
[Formula 2]
-[Al(R19)-O]n-
In formula (2), R19 is a halogen radical or a hydrocarbyl radical having 1 to 20 carbon atoms substituted or unsubstituted with halogen; n is an integer greater than or equal to 2,
[Formula 3]
A(R20) ₃
In formula (3), A is aluminum or boron; R20 is the same as or different from each other, and each independently represents a halogen radical or a hydrocarbyl radical having 1 to 20 carbon atoms substituted or unsubstituted with halogen,
[Formula 4]
[LH] ⁺ [Z(B) ₄ ] ^- or [L] ⁺ [Z(B) ₄ ] ^-
In formula (4), L is a neutral or cationic Lewis acid; H is a hydrogen atom;
Z is a group 13 element; B is each independently an aryl or alkyl radical having 6 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a halogen element, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group, or a phenoxy radical. According to claim 1,
At least one of R1, R2, R3 and R4 is hydrogen, and the rest are each independently (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₆ -C ₂₀ )aryl group or a (C ₁ -C ₂₀ )silyl group with or without an acetal group, a ketal group, or an ether group; R1, R2, R3 and R4 At least two of them may be linked to each other to form an aliphatic ring or an aromatic ring. According to claim 1,
At least one of R1, R2, R3 and R4 is hydrogen, and the rest are independently (C ₁ -C ₂₀ ) A polypropylene resin composition, characterized in that it is an alkyl group. According to claim 1,
At least two or more of R1, R2, R3 and R4 are hydrogen, and the rest are each independently (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₆ -C ₂₀ )aryl group or a (C ₁ -C ₂₀ )silyl group with or without an acetal group, a ketal group, or an ether group; Two of R1, R2, R3 and R4 are connected to each other to form an aliphatic ring or an aromatic ring. According to claim 1,
At least two or more of R1, R2, R3 and R4 are hydrogen, and the rest are each independently (C ₁ -C ₂₀ ) A polypropylene resin composition, characterized in that it is an alkyl group. According to claim 1,
The aluminum compound cocatalyst is one or a mixture of two or more selected from alkylaluminoxane or organoaluminum, and is selected from methylaluminoxane, tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum, and trioctylaluminum. alone or a mixture of two or more, the boron compound cocatalyst is tris(pentafluorophenyl)borane, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and triphenylmethylinium tetrakis(pentafluorophenyl) ) A polypropylene resin composition, characterized in that it is selected from borate alone or a mixture thereof. delete delete delete delete