KR101579615B1 - Polypropylene based resin composition and molded article using the same - Google Patents

Abstract

The present invention relates to a polyolefin having a molecular weight distribution of 1.5 to 3.0 and a BGN (Branch Gradient Number) value of 0.01 to 1; And a polypropylene resin composition and a molded article produced therefrom. INDUSTRIAL APPLICABILITY According to the present invention, there can be provided a polypropylene resin composition excellent in mechanical properties and impact strength and a molded article produced therefrom.

Description

TECHNICAL FIELD [0001] The present invention relates to a polypropylene resin composition and a molded article thereof,

The present invention relates to a polypropylene resin composition and a molded article produced from the polypropylene resin composition. More particularly, the present invention relates to a polypropylene resin composition having improved impact strength and mechanical properties by including a polyolefin having a narrow molecular weight distribution, The present invention relates to a molded article.

In general, a composition for automobile interior and exterior parts has been made of a polypropylene resin composition containing polypropylene (PP) as a main component and an impact modifier and an inorganic filler.

EPR or EPDM was mainly used as an impact modifier in most polypropylene resin compositions as a material for automotive interior and exterior materials, particularly bumper covers, before the development of ethylene-α-olefin copolymers polymerized by applying metallocene catalysts. Respectively. However, after the appearance of the ethylene-? -Olefin copolymer produced by the metallocene catalyst, the ethylene-? -Olefin copolymer has been used as an impact modifier and has become mainstream at present. This is because polypropylene-based composites using the polypropylene composite material have well-balanced physical properties such as impact strength, elastic modulus and flexural strength, and have good moldability and low cost.

The polyolefin synthesized by the metallocene catalyst has a narrow molecular weight distribution and good mechanical properties because the molecular structure is uniformly controlled by the Ziegler-Natta catalyst. The ethylene elastomer having a low density polymerized by the metallocene catalyst is also advantageous in that the? -Olefin copolymerized monomer is inserted relatively uniformly into the polyethylene (PE) molecule rather than by the Ziegler-Natta catalyst, And has good physical properties.

Dow has published [Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (CGC) in the early 1990s (US Pat. No. 5,064,802). In the copolymerization of ethylene and alpha olefins, the CGC Compared with the known metallocene catalysts, the excellent aspects of the CGC are summarized as follows: (1) high molecular weight copolymers with high activity at high polymerization temperatures and (2) - It is also excellent for the copolymerization of α-olefins with large steric hindrance such as hexene and 1-octene. In addition, as the various characteristics of CGC are gradually known during the polymerization reaction, efforts to synthesize the derivatives and use them as polymerization catalysts have been actively made in academia and industry.

One approach is to synthesize and incorporate a variety of metal compounds into which various bridges and nitrogen substituents have been introduced instead of silicon bridges. Opening exemplary metal compounds known to date are as follows (Chem. Rev. 2003, 103 , 283).

The compounds shown in the figure have been introduced with phosphorus (1), ethylene or propylene (2), methylidene (3) and methylene (4) bridges in place of the silicon bridge of the CGC structure, but ethylene polymerization or ethylene and alpha olefins The copolymer did not exhibit excellent results in terms of polymerization activity or copolymerization performance as compared with CGC.

As another approach, a large amount of compounds composed of oxydolides were synthesized instead of the amido ligands of CGC, and some polymerization using the compounds was attempted.

Of all these attempts, however, only a few catalysts have actually been applied to commercial plants. The copolymers of ethylene and alpha olefins polymerized using most transition metal compounds exhibit a narrow molecular weight distribution as compared to LDPE obtained through conventional high pressure processes, but in terms of polymer structure, they do not include long chain bases, Lt; RTI ID = 0.0 > branched < / RTI > branches. In recent years, attempts to obtain a polyolefin-based copolymer having a long chain branching polymer structure and various properties have been actively conducted in academia and industry, and development of new catalysts and processes therefor is still required.

The present invention is to provide a polypropylene resin composition including a polyolefin having a narrow molecular weight distribution and excellent mechanical properties, and having improved impact strength at room temperature and low temperature and excellent mechanical properties.

According to an aspect of the present invention, there is provided a polyolefin having a molecular weight distribution of 1.5 to 3.0 and a BGN (Branch Gradient Number) value of 0.01 to 1 calculated by the following formula 1: And a polypropylene resin composition comprising:

[Formula 1]

In Equation (1)

When a molecular weight distribution curve is drawn with the logarithm (log Mw) of the molecular weight (Mw) as the x-axis and the molecular weight distribution (dwt / dlog Mw)

The side chain content of the low molecular weight means the side branch content (branch content of 2 or more carbon atoms per 1,000 carbon atoms, unit: 1,000C) at the left boundary of 80% of the total area except 10% at the left and right ends, The side chain content of high molecular weight means the side chain content at the right border.

Another aspect of the present invention provides a molded article produced from the polypropylene resin composition.

According to the polypropylene resin composition of the present invention, a composition comprising a polyolefin having a narrow molecular weight distribution as an impact modifier and having excellent mechanical properties, and a composition containing the polyolefin are excellent in impact resistance and elasticity, It can be used in various fields.

1 is a graph showing the results of GPC-FTIR measurement of the polyolefin of Production Example 1. Fig.
2 is a graph showing the results of GPC-FTIR measurement of the polyolefin of Production Example 2. Fig.
3 is a graph showing the results of GPC-FTIR measurement of the polyolefin of Comparative Production Example 1. Fig.

In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

Moreover, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the polypropylene resin composition according to a specific embodiment of the present invention will be described in detail.

According to an embodiment of the present invention, a polyolefin having a BGN (Branch Gradient Number) value of 0.01 to 1 calculated by the following formula 1 is 1.5 to 3.0; And a polypropylene resin composition comprising:

[Formula 1]

In the term BGN (Branch Gradient Number) used in the specification of the present invention, BGN is a measure showing how the content of comonomer such as alpha olefin is distributed according to molecular weight. The branched branch as referred to in the BGN is a branched chain derived from the alpha olefin such as propylene, 1-butene, 1-hexene, 1-octene and the like as a comonomer in the polyolefin polymerization process. It means side branches. The side branch includes both a short carbon branch (SCB) having 2 to 6 carbon atoms and an LCB (long carbon branch) having 7 or more carbon atoms.

Using GPC-FTIR equipment, molecular weight, molecular weight distribution and side-chain content can be measured simultaneously and continuously.

The value of the BGN (Branch Gradient Number) is determined by continuously measuring the molecular weight, the molecular weight distribution and the side chain content by using GPC-FTIR equipment and setting the log value (log Mw) of the molecular weight (Mw) (Dwt / dlog Mw) is plotted on the y-axis, the molecular weight distribution curve of the low molecular weight is calculated by subtracting the side branch content of 80% of the left boundary from the total area : Number / 1,000C), and the side chain content of the high molecular weight means the value calculated by the following formula 1 with the side chain content at the right border of the middle 80%. Here, the content of the side branches means the side branch content of 2 or more carbon atoms per 1,000 carbon atoms.

[Formula 1]

When the BGN value is a positive value, it means that the side chain content is low in the low molecular weight region according to the molecular weight distribution curve to the logarithm of the molecular weight and the side chain content is relatively high in the high molecular weight region. On the other hand, The value of negative (-) means that the side chain content is high in the low molecular weight region and the side chain content is relatively low in the high molecular weight region.

The polyolefin contained in the polypropylene resin composition of the present invention has a BGN value measured and calculated as described above of 0.01 to 1.0, or about 0.01 to about 0.9, or about 0.01 to about 0.5, or about 0.01 to about 0.2, Or from about 0.01 to about 0.1, or from about 0.03 to about 0.1. That is, the polyolefin of the present invention is characterized in that it has a low side chain content in a low molecular weight region and a relatively high side chain content in a high molecular weight region, and the slope thereof is within the above-mentioned range.

When the BGN value is in the above range and a narrow molecular weight distribution is satisfied at the same time, high impact strength and good mechanical properties can be achieved when the properties of the polyolefin are optimized and compounded with a polypropylene resin.

The polyolefin contained in the polypropylene resin composition of the present invention may have a range of the number of side branches of 2 or more carbon atoms per 1,000 carbon atoms of about 20 to about 120, preferably about 50 to about 100.

The polyolefin contained in the polypropylene resin composition of the present invention may also have a molecular weight distribution (weight average molecular weight / number average molecular weight) of from about 1.0 to about 3.0, or from about 1.5 to about 3.0, or from about 1.5 to about 2.8, About 2.8. As described above, the polyolefin of the present invention has a very narrow molecular weight distribution and can exhibit high impact strength.

The polyolefin preferably has a melt flow index (MI) of from about 0.1 to about 2000 g / 10 min, preferably from about 0.1 to about 1000 g / 10 min, more preferably from about 0.1 to about 1000 g / 10 min, measured under a load of 2.16 kg at 190 캜 according to ASTM D1238 May be about 0.1 to 500 g / 10 min, but is not limited thereto.

In addition, the melt flow rate ratio (MFRR) of the polyolefin may be from about 5 to about 15, preferably from about 6 to about 13, but is not limited thereto.

Also, the density of the polyolefin may be from about 0.85 to about 0.91 g / cc, preferably from about 0.86 to about 0.91 g / cc, more preferably from about 0.86 to about 0.90 g / cc, It is not.

However, when the melt flow index, the melt flow rate ratio, the density, and the like are within the above-mentioned ranges, the physical properties are more optimized and high impact strength and good mechanical properties can be achieved.

The polyolefin contained in the polypropylene resin composition of the present invention is preferably a copolymer of ethylene and an alpha olefin comonomer which is an olefinic monomer.

The alpha olefin comonomer may be an alpha olefin having 3 or more carbon atoms. Examples of the alpha olefin having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, , 1-tetradecene, 1-hexadecene, 1-octadecene or 1-eicosene.

In the copolymer of the ethylene and alpha olefinic comonomers, the alpha olefin comonomer content is from about 5 to about 70 wt%, preferably from about 5 to about 60 wt%, more preferably from about 10 to about 50 wt% %. ≪ / RTI >

The weight average molecular weight of the polyolefin may be from about 10,000 to about 500,000 g / mol, preferably from about 20,000 to about 200,000 g / mol, but is not limited thereto.

The polyolefin as described above has excellent impact strength when mixed with other polymers and can be used in various fields such as household articles, automobiles, and shock absorbers.

The polyolefin according to the present invention having the above-mentioned characteristics can be obtained by copolymerization with ethylene and an alpha olefin using a mixed metallocene compound containing two metallocene compounds having different structures as a catalyst, The molecular weight distribution and the BGN value as described above.

More specifically, the polyolefin comprises a first metallocene compound represented by the following formula (1); And a second metallocene compound represented by the following formula (2): < EMI ID = 2.0 >

[Chemical Formula 1]

In Formula 1,

R1 and R2 may be the same or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid of a Group 4 metal substituted with hydrocarbyl; The R1 and R2 or the two R2's may be linked to each other to form a ring by alkyl having 1 to 20 carbon atoms or alkylidene having 6 to 20 carbon atoms;

R3, R3 'and R3 "may be the same or different from each other and each independently represents hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkyl of 7 to 20 carbon atoms An aryl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an amido group, two or more of R3, R3 'and R3' An aromatic ring may be formed;

CY is a substituted or unsubstituted aliphatic or aromatic ring, the substituent on CY is selected from the group consisting of halogen; 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; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an alkylamido group having 1 to 20 carbon atoms; An arylamido group having 6 to 20 carbon atoms, and when the number of the substituents is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;

M1 is a Group 4 transition metal;

Q1 and Q2 may be the same or different from each other and are each independently halogen; 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; Arylalkyl having 7 to 20 carbon atoms; Alkylamido of 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene of 1 to 20 carbon atoms;

(2)

In Formula 2,

M2 is a Group 4 transition metal;

Q3 and Q4 may be the same or different from each other and are each independently halogen; 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; Arylalkyl having 7 to 20 carbon atoms; Alkylamido of 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene of 1 to 20 carbon atoms;

R4 to R10 may be the same or different from each other, and each independently hydrogen; Alkyl having 1 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; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Or alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms;

B is carbon, silicon, or germanium, cyclopentadienyl-based ligand and JR10 _{-y z} for a bridge that binds by covalent bonds;

J is a Group 15 element or a Group 16 element of the periodic table;

z is the oxidation number of the element J;

y is the combined number of J elements;

n is an integer of 0 to 10;

When the ethylene and alpha olefin comonomers are polymerized using the hybrid metallocene catalyst comprising the first metallocene compound of Formula 1 and the second metallocene compound of Formula 2, A polyolefin having a low side-chain content and a relatively high side-branch content in a high molecular weight region can be obtained.

On the other hand, the polymerization reaction of the ethylene and alpha olefin comonomers can be carried out at about 130 to about 250 ° C, preferably about 140 to about 200 ° C. When the second metallocene compound is used in admixture with the first metallocene compound, the activity of the catalyst can be maintained even in the synthesis process at a high temperature of 130 ° C or higher. In the synthesis reaction of the polyolefin, .

The polymerization reaction of the ethylene and the alpha olefin comonomer may be carried out in a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, or an emulsion polymerization process, but is preferably carried out in a solution polymerization reaction in a single reactor Can be done. In the method for producing polyolefin, polyolefin can be synthesized in a single reactor even though two different metallocene catalysts are used, so that a simple manufacturing process can be configured to reduce the processing time and cost.

Specific examples of the first metallocene compound represented by the formula (1) include compounds represented by the following formulas (3) and (4), but are not limited thereto.

 (3)

In Formula 3,

R1, R2, Q1, Q2 and M1 are the same as defined in Formula 1,

And R11 may be the same or different from each other, and each independently hydrogen; halogen; 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; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an amido group; Two or more of the R < 11 > s may be connected to each other to form an aliphatic ring or an aromatic ring.

 [Chemical Formula 4]

In Formula 4,

R1, R2, Q1, Q2, and M1 are the same as defined in Formula 1,

R12 may be the same or different from each other, and each independently hydrogen; halogen; 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; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an amido group; Two or more of the R < 12 > s may be connected to each other to form an aliphatic ring or an aromatic ring.

Specific examples of the more preferred compounds for controlling the electronic stereoscopic environment around the metal in the compound of Formula 1 are as follows.

In the following formulas, R2 may independently be hydrogen or a methyl group, and Q1 or Q2 may be the same or different from each other, and each independently may be a methyl group, a dimethylamido group or a chloride group.

Specific examples of the second metallocene compound of Formula 2 include, but are not limited to, the following compounds.

According to an embodiment of the present invention, in the method for producing a polyolefin, the hybrid metallocene catalyst may further include a cocatalyst compound in addition to the first and second metallocene compounds described above.

The promoter compound includes a Group 13 metal of the periodic table and may be at least one selected from the group consisting of compounds represented by the following general formulas (5), (6) and (7)

 [Chemical Formula 5]

- [Al (R13) -O] c-

In the general formula (5), R 13 is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more,

[Chemical Formula 6]

D (R14) ₃

In Formula 6,

D is aluminum or boron, R14 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

(7)

[LH] ⁺ [ZE ₄ ] ^- or [L] ⁺ [ZE ₄ ] ^-

In Formula 7,

L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 element, and E may be the same or different and each independently represents a hydrogen atom, a halogen atom, An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with phenoxy.

Examples of the compound represented by Formula 5 include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like.

Examples of the alkyl metal compound represented by Formula 6 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethyl Tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, Dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like can be used.

Examples of the compound represented by Formula 7 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p (O, p-dimethylphenyl) boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, trimethylammoniumtetra (P-trifluoromethylphenyl) boron, tetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p -trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N , N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphor Tetramethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra (aluminum) (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl) Aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapenta Triphenyl aluminum, diethyl ammonium aluminum tetrapentafluorophenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl (P-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, and the like can be used in the present invention. have.

Also, the content of the cocatalyst is in the range of about 1 to about 10,000, preferably about 1 to about 1,000, more preferably about 1 To about 500. < RTI ID = 0.0 > If the molar ratio is less than 1, the effect of addition of the cocatalyst is insufficient. If the molar ratio is more than 10,000, excess alkyl groups or the like which are not involved in the reaction may interfere with the catalytic reaction and act as catalyst poisons. Side reaction may proceed and excess aluminum or boron may remain in the polymer.

In the preparation of the mixed metallocene catalyst, hydrocarbon solvents such as pentane, hexane, heptane and the like, aromatic solvents such as benzene and toluene may be used as a reaction solvent, but not always limited thereto, and all A solvent may be used.

In the process for producing the polyolefin, the hybrid metallocene catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane and isomers thereof, , A hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, chlorobenzene, or the like. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

The polyolefin having the above-mentioned molecular weight distribution and BGN value can be produced using the hybrid metallocene catalyst. Copolymerization with alpha olefins in the case of hybrid metallocene catalysts is induced by a second metallocene compound, which in particular makes up the high molecular weight moiety, which has a narrow molecular weight distribution and in which the alpha olefin comonomer is more bonded to the high molecular weight chain side Thereby making it possible to produce a high-performance polyolefin.

The preparation of the polyolefin may be carried out by solution polymerization, and may be carried out according to a conventional method, for example, by continuously feeding ethylene and an alpha-olefin comonomer at a constant ratio.

When the alpha olefin is copolymerized with ethylene as a comonomer using the mixed metallocene catalyst, the alpha olefin comonomer is preferably selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl- Hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene or 1-eicosene. But is not limited to.

The polymerization temperature when copolymerizing ethylene with the alpha olefin as the comonomer using the hybrid metallocene catalyst may be in the range of about 130 to about 250 ° C, preferably about 140 to about 200 ° C. As described above, when the second metallocene compound is used in admixture with the first metallocene compound, the activity of the catalyst can be maintained even at a high temperature of 130 ° C or higher. Therefore, in the synthesis reaction of the polyolefin, Thereby making the active point 2 or more. In particular, since the metallocene catalyst for synthesis of high-density polyolefins is low in activity at a high temperature range, it is generally not used in a solution polymerization step in which a high reaction temperature is applied, but the second metallocene compound of the above formula (2) When mixed with the first metallocene compound, excellent catalytic activity can be exhibited even in a high temperature range of 130 ° C or higher.

Also, the polymerization pressure is preferably carried out at about 1 to about 150 bar, more preferably about 1 to about 120 bar, most preferably about 10 to about 120 bar.

Meanwhile, in the polymerization reaction of the ethylene and alpha-olefin comonomers, the physical properties of the polyolefin prepared by controlling the content of the second metallocene compound can be controlled.

In particular, the hybrid metallocene catalyst contains a relatively low content of the second metallocene compound. More specifically, the second metallocene compound is present in an amount greater than 0 mol% to less than about 50 mol%, preferably about 5 to about 30 mol%, based on the total amount of the first and second metallocene compounds, And more preferably from about 5 to about 25 mol%. When the second metallocene compound is contained in such a content ratio, a polyolefin having a narrow molecular weight distribution and a BGN value in the above-described range can be provided.

example The polypropylene contained in the resin composition of the present invention is not particularly limited in its production method and kind, and polypropylene that is commonly used in the art to which the present invention belongs may be used. For example, highly crystalline homopolypropylene, a block copolymer containing ethylene, or a mixture thereof can be used.

The polypropylene resin composition according to the present invention may further contain additives such as an inorganic filler, an antioxidant, a UV stabilizer, and a slip agent as other additives.

In the present invention, by using the above-mentioned polypropylene resin composition, the impact strength at normal temperature and low temperature is improved, and a resin composition of excellent physical properties which does not deteriorate the mechanical properties such as elastic modulus and tensile strength can be provided.

The polypropylene resin composition according to the present invention may contain about 5 to about 50 parts by weight, preferably about 10 to about 30 parts by weight, of the polyolefin with respect to 100 parts by weight of the total resin composition, To about 95 parts by weight, preferably from about 70 to about 90 parts by weight. If the amount of the polyolefin is too small, the impact strength may be reduced. If the polyolefin is contained too much, mechanical properties may be deteriorated.

According to one embodiment of the present invention, the polypropylene resin composition has an Izod impact strength of about 12 kgm / m or more, for example, about 12 to about 50 kg / m, measured at 23 ° C in accordance with ASTM D256, m, or from about 12 to about 40 kgm / m, and the Izod impact strength measured at -20 캜 according to ASTM D256 is at least about 5 kgm / m, such as from about 5 to about 15 kgm / m , Or from about 5 to about 10 kgm / m, and can exhibit excellent impact strength at normal temperature and low temperature.

According to another aspect of the present invention, there is provided a molded article produced using the above-mentioned polypropylene resin composition.

By using the above-mentioned polypropylene resin composition, the molded article of the present invention can exhibit excellent physical properties such that the impact strength at room temperature and low temperature is improved, and mechanical properties such as elastic modulus and tensile strength are not deteriorated. The production method of the molded article may be any technique known in the art such as injection molding, extrusion molding and the like, and is not particularly limited.

The molded article which can be produced by using the polypropylene resin composition is not limited to the type as long as it can be produced by using a polypropylene resin composition. Examples of the molded article include all kinds of articles such as household articles, automobile bumper covers, Automobile parts such as a glove box and a pillar.

The molded article produced using the polypropylene resin composition according to the present invention is excellent in impact strength, tensile strength, flexural strength, flexural modulus and shrinkage, and can be used in various fields such as household articles, automobiles, and shock absorbers .

The present invention will be described in more detail in the following Examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Example >

Metallocene  Compound Synthetic example

Synthetic example  1: 1st Metallocene  Synthesis of compounds

Synthetic example  1-1

8- (2,3,4,5- Tetramethyl -1,3- Cyclopentadienyl ) -1,2,3,4-tetrahydroquinoline ((8- (2,3,4,5-Tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline)

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a Schlenk flask. The Schlenk flask was immersed in a -78 ° C low-temperature bath made of dry ice and acetone and stirred for 30 minutes. Subsequently, n-BuLi (n-butyllithium, 39.3 mL, 2.5M, 98.24 mmol) was added via syringe under a nitrogen atmosphere to form a pale yellow slurry. Then, after the flask was stirred for 2 hours, the temperature of the flask was raised to room temperature while removing the produced butane gas. The flask was again immersed in a low-temperature bath at -78 ° C, the temperature was lowered, and then CO ₂ gas was introduced. As the carbon dioxide gas was introduced, the slurry disappeared and became a clear solution. The flask was connected to a bubbler to remove the carbon dioxide gas and raise the temperature to room temperature. After that, excess CO ₂ gas and solvent were removed under vacuum. The flask was transferred to a dry box, and pentane was added thereto, followed by vigorous stirring and filtration to obtain a lithium carbamate of a white solid compound. The white solid compound is coordinated with diethyl ether. The yield is 100%.

^{1 H NMR (C6D6, C5D5N)} : 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 (C6D6): [delta] 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09 (C = O) ppm.

The lithium carbamate compound prepared above (8.47 g, 42.60 mmol) was placed in a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were added in sequence. The Schlenk flask was immersed in acetone and a small amount of dry ice at -20 ° C in a low temperature bath and stirred for 30 minutes. Then, tert-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture turned red. The mixture was stirred for 6 hours while keeping the temperature at -20 ° C. Of CeCl ₃ · 2LiCl solution (129 mL, 0.33 M, 42.60 mmol) and tetra methyl cyclo non-pentynyl (5.89 g, 42.60 mmol) dissolved in tetrahydrofuran was added to the flask under a given mixture in the syringe, and then, in a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature. After 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Subsequently, water (15 mL) was added to the flask, and ethyl acetate was added thereto, followed by filtration to obtain a filtrate. The filtrate was transferred to a separatory funnel, followed by addition of hydrochloric acid (2N, 80 mL) and shaking for 12 minutes. A saturated aqueous solution of sodium hydrogencarbonate (160 mL) was added to neutralize the solution, and then the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture, followed by filtration, and the filtrate was taken to remove the solvent. The obtained filtrate was purified by column chromatography using hexane and ethyl acetate (v / v, 10: 1) to obtain yellow oil. The yield was 40%.

^{1 H NMR (C6D6): 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, IH, Cp-H), 3.76 (br s, IH, NH), 6.77 (t, J = 7.2 Hz, 1H, quin- , quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm.

Synthetic example  1-2

[(1,2,3,4- Tetrahydroquinoline -8-yl) Tetramethylcyclopentadienyl - Eta 5 , Kappa-N] Titanium dimethyl ) ([(1,2,3,4- Tetrahydroquinoline -8-yl) tetramethylcyclopentadienyl-ethyl] -5, kapa-N] titanium dimethyl ) Synthesis of

In a dry box, the compound (8.07 g, 32.0 mmol) synthesized in Synthesis Example 1-1 and 140 mL of diethyl ether were placed in a round flask, the temperature was lowered to -30 캜, and n-BuLi (17.7 g, 2.5 M , 64.0 mmol) was slowly added with stirring. The reaction was allowed to proceed for 6 hours while the temperature was raised to room temperature. Thereafter, the solid was obtained by filtration while washing with diethyl ether several times. Vacuum was applied to remove the remaining solvent to obtain a yellow solid di-lithium compound (9.83 g). The yield was 95%.

^{1 H NMR (C6D6, C5D5N)} : 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 ppm.

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 MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added with stirring at -30 ° C. [(1, 2, 3, 4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-ether 5, 2,3,4-Tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, kapa-N] dilithium) (5.30 g, 15.76 mmol) were placed in a flask. The mixture was stirred for 3 hours while the temperature was raised to room temperature. After completion of the reaction, the solvent was removed by vacuum, dissolved in pentane, and filtered to remove the filtrate. Vacuum was applied to remove the pentane to obtain a dark brown compound (3.70 g). The yield was 71.3%.

^{1 H NMR (C6D6): 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 (C6D6):? 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.

Synthetic example  2: 2nd Metallocene  Synthesis of compounds

[ methyl (6-t- butoxyhexyl ) silyl (? ⁵ - tetramethylCp ) (t- Butylamido )] TiCl ₂ Manufacturing

50 g of Mg (s) was added to the 10 L reactor at room temperature, and then 300 mL of THF was added. After adding 0.5 g of I ₂ , the reactor temperature was maintained at 50 ° C. After the reactor temperature stabilized, 250 g of 6-t-buthoxyhexyl chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. By adding 6-t-butoxyhexyl chloride, it was observed that the temperature of the reactor was increased by 4 ~ 5 ° C. The mixture was stirred for 12 hours while continuously adding 6-t-butoxyhexyl chloride. After 12 hours of reaction, a black reaction solution was obtained. 2 mL of the resulting black solution was added, and water was added thereto. An organic layer was obtained, and 6-t-buthoxyhexane was confirmed by ¹ H-NMR. From 6-t-butoxyhexane It was found that the Grignard reaction proceeded well. Thus, 6-t-buthoxyhexyl magnesium chloride was synthesized.

500 g of MeSiCl ₃ and 1 L of THF were added to the reactor and the reactor temperature was cooled to -20 ° C. 560 g of synthesized 6-t-butoxyhexylmagnesium chloride was added to the reactor at a rate of 5 mL / min using an injection pump. After the injection of the Grignard reagent, the reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, it was confirmed that MgCl ₂ salt of white was formed. 4 L of hexane was added thereto, and the salt solution was removed through a laboratory pressurized dehydration filtration apparatus (labdori, Han River Engineering Co., Ltd.) to obtain a filter solution. The resulting filter solution was added to the reactor, and hexane was removed at 70 ° C to obtain a pale yellow liquid. The resulting liquid was confirmed to be the desired methyl (6-t-butoxyhexyl) dichlorosilane compound by ¹ H-NMR.

¹ H-NMR (CDCl ₃ ): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H)

After 1.2 moles (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, the reactor temperature was cooled to -20 占 폚. 480 mL of n-BuLi was added to the reactor at a rate of 5 mL / min using an injection pump. After the addition of n-BuLi, the reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, an equivalent amount of Methyl (6-t-butoxy hexyl) dichlorosilane (326 g, 350 mL) was rapidly added to the reactor. After the reactor temperature was slowly raised to room temperature, the mixture was stirred for 12 hours. After the reactor was cooled to 0 ° C, 2 equivalents of t-BuNH ₂ was added. The reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, THF was removed and 4 L of hexane was added to obtain a filter solution from which the salt was removed through labdori. The filter solution was added to the reactor again, and hexane was removed at 70 ° C to obtain a yellow solution. The obtained yellow solution was confirmed to be methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane compound by ¹ H-NMR.

TiCl ₃ (THF) ₃ (10 mmol) was rapidly added to the dilithium salt of the ligand synthesized from n-BuLi and a ligand Dimethyl (tetramethylCpH) t-Butylaminosilane in THF solution. The reaction solution was agitated for 12 hours while slowly raising the temperature to -78 ° C. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution with a blue color was obtained. THF was removed from the resulting reaction solution, and hexane was added to filter the product. After removal of hexane from the obtained filter solution, ¹ H-NMR confirmed that the desired compound was methyl [6-t-buthoxyhexyl] silyl (η ⁵ -tetramethylCp) (t-Butylamido)] TiCl ₂ .

¹ H-NMR (CDCl ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H) , 0.7 (s, 3H)

Polyolefin Manufacturing example

Manufacturing example  One

A 2L autoclave continuous process reactor was charged with a hexane solvent (5.38 kg / h) and 1-butene (0.82 kg / h), and the temperature at the top of the reactor was preheated to 160 ° C. (0.45 占 퐉 ol / min), the second metallocene compound (0.05 占 퐉 ol / min) and dimethylanilinium tetrakis (penta Fluorophenyl) borate promoter (1.5 μmol / min) were simultaneously introduced into the reactor. Ethylene (0.87 kg / h) was then fed into the autoclave reactor and maintained at 160 캜 for 30 minutes or more at a pressure of 89 bar in a continuous process, followed by copolymerization to obtain a copolymer. Next, the remaining ethylene gas was taken out, and the polymer solution was dried in a vacuum oven for 12 hours or more, and the physical properties were measured.

Manufacturing example  2

A 2L autoclave continuous process reactor was charged with a hexane solvent (5.9 kg / h) and 1-butene (1.01 kg / h), and then the temperature at the top of the reactor was preheated to 160 ° C. (0.4 mmol / min), the second metallocene compound (0.1 μmol / min), and dimethylanilinium tetrakis (pentaerythritol tetrakis Fluorophenyl) borate promoter (1.5 μmol / min) were simultaneously introduced into the reactor. Ethylene (1.0 kg / h) was then fed into the autoclave reactor and maintained at 160 캜 for 30 minutes or more at a pressure of 89 bar in a continuous process, followed by copolymerization to obtain a copolymer. Next, the remaining ethylene gas was taken out, and the polymer solution was dried in a vacuum oven for 12 hours or more, and the physical properties were measured.

compare Manufacturing example  One

An ethylene-1-butene copolymer (product name: LC565) of LG Chem manufactured using only the first metallocene catalyst was prepared.

Polypropylene series  Preparation of resin composition Example

Example  One

90% by weight of M1600 (MI = 25, ASTM D1238) of LG Chem as polypropylene, and 10% by weight of the polyolefin obtained in Preparation Example 1 were mixed.

In order to prepare a sphin for analysis of physical properties, the mixture was uniformly mixed using a Henschel mixer, followed by pelletizing using a co-rotating twin screw extruder to prepare a specimen using an injection machine . The physical properties of the prepared specimen are shown in Table 2 below.

Example  2

The compositions and specimens were prepared in the same manner as in Example 1 except for using 80% by weight of M1600 of LG Chemical as polypropylene and 20% by weight of the polyolefin obtained in Preparation Example 1, and the properties were measured.

Example  3

The compositions and specimens were prepared and measured for physical properties in the same manner as in Example 1, except that 80% by weight of M1600 of LG Chemical as polypropylene and 20% by weight of the polyolefin obtained in Preparation Example 2 were used.

Comparative Example  One

Except that 90 wt% of M1600 of LG Chem as the polypropylene and 10 wt% of LC565 (ethylene-1-butene copolymer, density 0.865 g / cc, MI 4.6, PDI 2.32) of LG Chemical of Comparative Preparation Example 1 were used The compositions and specimens were prepared in the same manner as in Example 1, and the physical properties were measured.

Comparative Example  2

The compositions and specimens were prepared in the same manner as in Example 1 except for using 80 wt% of M1600 of LG Chemical as polypropylene and 20 wt% of LC565 of LG Chemistry of Comparative Preparation Example 1, and physical properties were measured.

< Experimental Example >

Polyolefin  Property measurement

In the following manner Physical properties of the polyolefins of Production Examples 1 and 2 and Comparative Production Example 1 were measured and are shown in Table 1 below.

1) Density: ASTM 1505

2) Melt flow index (MI, 2.16 kg / 10 min): Measuring temperature 190 캜, ASTM 1238

3) Molecular weight and molecular weight distribution: The number-average molecular weight, the weight-average molecular weight and the Z-average molecular weight were measured using Gel Permeation Chromatography-FTIR (GPC-FTIR) The molecular weight distribution is represented by the ratio of the weight average molecular weight to the number average molecular weight.

4) BGN (Branch Gradient Number): When the log value (log Mw) of the molecular weight (Mw) in the GPC-FTIR measurement result is represented by x-axis and the molecular weight distribution (dwt / dlog Mw) When the molecular weight distribution curve is plotted on the axis, the side branch content of the low molecular weight is defined as the side branch content (unit: number / 1,000C) at the left boundary of 80% of the total area excluding the left and right ends of 10% The BGN value was obtained by calculating the value of the content as the side-branch content at the right boundary of the middle 80%, as shown in the following formula (1).

 [Formula 1]

density
(Unit: g / cc) Melt Index (MI)
(Unit: g / 10 min) Molecular weight distribution Weight average molecular weight
(g / mol) BGN Production Example 1 0.865 4.5 2.31 91,791 0.05 Production Example 2 0.865 5.0 2.35 89,912 0.06 Comparative Preparation Example 1 0.865 4.6 2.32 86,610 0

The results of GPC-FTIR measurement of the polyolefins of Production Example 1, Production Example 2 and Comparative Production Example 1 are shown in Figs. 1 to 3, respectively.

1 and 2, the side branch content of 2 or more carbon atoms at the left boundary point (point A) in the middle 80% region of the molecular weight distribution curve area and the side branch content of 2 or more carbon atoms at the right boundary point (point B) It can be confirmed that the BGN value calculated according to the above 1 has a positive value.

However, referring to FIG. 3, the polyolefin of Comparative Preparation Example 1 showed a BGN value close to zero, indicating that it did not show the characteristic comonomer distribution as in the present invention.

Polypropylene series  Measurement of physical properties of resin composition

The physical properties of the compositions of Examples and Comparative Examples were measured according to the following measurement methods.

1) Melt Index (MI, 2.16 kg / 10 min): ASTM D1238, 2.16 kg, 190 DEG C

2) Flexural Strength: ASTM D790, 1/4 ", 10 mm / min

3) Flexural Modulus: ASTM D790, 1/4 ", 10 mm / min

4) Izod Impact Strength (IZOD, @ 23 ° C): ASTM D256, 1/4 "at 23 ° C mm / min

5) Izod Impact Strength (IZOD, @ -20 ° C): ASTM D256, 1/4 "at -20 ° C mm / min

6) Shrinkage ratio: The specimens were prepared by injection molding in a mold having a length of 130 mm and then stored at room temperature for 12 hours or more. After 12 hours, the length of the specimen was measured and the shrinkage percentage was calculated according to the following formula.

Shrinkage percentage (%) = (130-measurement length) / 130 * 100

In the same manner as described above The properties of the specimens obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were measured and are shown in Table 2 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Type and content of polyolefin Production Example 1
10 wt% Production Example 1
20 wt% Production Example 2
20 wt% Comparative Preparation Example 1
10 wt% Comparative Preparation Example 1
20 wt% The melt index (2.16 kg, 230 &lt; 0 &gt; C) 23.69 21.64 21.3 25.39 21.41 Flexural Strength (kgf / cm ² ) 208 177 251 223 176 Flexural modulus (kgf / cm ² ) 9868 8112 8300 10436 7896 Izod impact strength
(@ 23 C) (kgm / m) 13.14 37.01 38.9 10.50 35.03 Izod impact strength
(@ -20 DEG C) (kgm / m) 5.40 6.82 7.0 4.86 6.00 Shrinkage (%) 12.82 10.34 9.1 12.79 10.71

Referring to Table 2, when the polyolefin having the same content was included, the composition of Example of the present invention exhibited improved impact strength and exhibited equivalent mechanical properties in other mechanical properties. Therefore, it can be usefully used for applications such as automobile interior and exterior materials requiring high impact strength.

Claims (12)

A polyolefin having a molecular weight distribution of 1.5 to 3.0 and a BGN (Branch Grade Number) value of 0.01 to 1 calculated by the following formula 1; And a polypropylene-based resin composition:
[Formula 1]

In Equation (1)
When a molecular weight distribution curve is drawn with the logarithm (log Mw) of the molecular weight (Mw) as the x-axis and the molecular weight distribution (dwt / dlog Mw)
The side chain content of the low molecular weight means the side branch content (branch content of 2 or more carbon atoms per 1,000 carbon atoms, unit: 1,000C) at the left boundary of 80% of the total area except 10% at the left and right ends, The side chain content of high molecular weight means the side chain content at the right border.
The polypropylene resin composition according to claim 1, wherein the polyolefin has a density of 0.85 to 0.91 g / cc.
The polypropylene resin composition according to claim 1, wherein the polyolefin has a side chain content of at least 2 carbon atoms per 1,000 carbon atoms of 20 to 120.
The polyolefin of claim 1, wherein the polyolefin is selected from the group consisting of ethylene and alpha-olefins, in the presence of a hybrid metallocene catalyst comprising a first metallocene compound represented by the following formula (1) and a second metallocene compound represented by the following formula A polypropylene resin composition obtained by polymerizing an olefin comonomer:
[Chemical Formula 1]

In Formula 1,
R1 and R2 may be the same or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid of a Group 4 metal substituted with hydrocarbyl; The R1 and R2 or the two R2's may be linked to each other to form a ring by alkyl having 1 to 20 carbon atoms or alkylidene having 6 to 20 carbon atoms;
R3, R3 'and R3 "may be the same or different from each other and each independently represents hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkyl of 7 to 20 carbon atoms An aryl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an amido group, two or more of R3, R3 'and R3' An aromatic ring may be formed;
CY is a substituted or unsubstituted aliphatic or aromatic ring, the substituent on CY is selected from the group consisting of halogen; 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; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an alkylamido group having 1 to 20 carbon atoms or an arylamido group having 6 to 20 carbon atoms; when the number of the substituents is plural, two or more substituents in the substituents may be connected to each other to form an aliphatic or aromatic ring;
M1 is a Group 4 transition metal;
Q1 and Q2 may be the same or different from each other and are each independently halogen; 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; Arylalkyl having 7 to 20 carbon atoms; Alkylamido of 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene of 1 to 20 carbon atoms;
(2)

In Formula 2,
M2 is a Group 4 transition metal;
Q3 and Q4 may be the same or different from each other and are each independently halogen; 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; Arylalkyl having 7 to 20 carbon atoms; Alkylamido of 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene of 1 to 20 carbon atoms;
R4 to R10 may be the same or different from each other, and each independently hydrogen; Alkyl having 1 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; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Or alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms;
B is carbon, silicon, or germanium, cyclopentadienyl-based ligand and JR10 _{-y z} for a bridge that binds by covalent bonds;
J is a Group 15 element or a Group 16 element of the periodic table;
z is the oxidation number of the element J;
y is the combined number of J elements;
n is an integer of 0 to 10;
5. The method of claim 4, wherein the hybrid metallocene catalyst comprises a polypropylene comprising greater than 0 mol% and less than 50 mol% of the second metallocene compound, based on the total amount of the first and second metallocene compounds Based resin composition.
5. The polypropylene resin composition according to claim 4, wherein the polymerization of ethylene and alpha olefin comonomers is carried out by a continuous solution polymerization process.
5. The polypropylene resin composition according to claim 4, wherein the hybrid metallocene catalyst further comprises at least one cocatalyst selected from compounds represented by the following formulas (5) to (7)
[Chemical Formula 5]
- [Al (R13) -O] c-
In the general formula (5), R 13 is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more,
[Chemical Formula 6]
D (R14) ₃
In Formula 6,
D is aluminum or boron, R14 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
(7)
[LH] ⁺ [ZE ₄ ] ^- or [L] ⁺ [ZE ₄ ] ^-
In Formula 7,
L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 element, and E may be the same or different and each independently represents a hydrogen atom, a halogen atom, An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with phenoxy.
The polypropylene resin composition according to claim 4, wherein the polymerization of ethylene and alpha olefin comonomers is carried out at 130 to 250 ° C.
5. The process of claim 4 wherein said alpha olefin comonomer is selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
The polypropylene resin composition according to claim 1, wherein the polypropylene is at least one selected from the group consisting of highly crystalline homopolypropylene, block copolymers containing ethylene, and mixtures thereof.
The polypropylene resin composition according to claim 1, wherein the polyolefin is contained in an amount of 5 to 50 parts by weight and the polypropylene is contained in an amount of 50 to 95 parts by weight.
A molded article produced by using the polypropylene resin composition according to any one of claims 1 to 11.

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