KR20200141950A - Propylene-ethylene random copolymer - Google Patents

Abstract

The present invention relates to a high-transparency propylene-ethylene random copolymer for injection, which has excellent processability while having low total volatile organic compound (TVOC) emissions, and has maximized the ethylene content.

Description

Propylene-ethylene random copolymer {PROPYLENE-ETHYLENE RANDOM COPOLYMER}

The present invention relates to a propylene-ethylene random copolymer.

Polypropylene is a general-purpose resin, which is easy to process and has excellent physical properties for the price, replacing traditional materials such as glass, wood, paper, metal, or other plastics and even engineering plastics. to be.

Recently, in order to manufacture an injection molded article requiring transparency, a method of randomly copolymerizing propylene with ethylene or butene or a method of ternary copolymerization has been studied. Among them, it is known that propylene having a high ethylene content is more effective as the biggest factor for transparency. However, compared to the conventional homopolypropylene, the crystallinity of the randomly copolymerized polypropylene decreases as the content of ethylene, which is a comonomer in the polymer, increases, and as a result, the balance between stiffness and impact strength is not maintained. It is difficult to ensure process stability.

On the other hand, catalysts for polypropylene polymerization can be largely classified into Ziegler Natta catalysts and metallocene catalysts. Since Ziegler Natta catalysts are multi-site catalysts having multiple active points, It is characterized by a wide molecular weight distribution, and there is a problem in that there is a limitation in securing desired physical properties because the composition distribution of the comonomer is not uniform. In particular, in the case of performing random copolymerization with ethylene for securing transparency in the presence of a Ziegler-Natta catalyst (Z/N, ziegler-natta), the polymerizability of ethylene is large, so that it is not a homogeneous polymer. , There is a problem in that a polymer is formed in which the ethylene polymer is formed as a block between the propylene polymers, which is not a repeating structure, so that physical properties are greatly deteriorated and the volatile organic compound emission amount (VOC) is high.

On the other hand, metallocene catalysts consist of a combination of a main catalyst composed of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum. Such a catalyst is a homogeneous complex catalyst and is a single site catalyst. It is possible to prepare a polymer having a narrow molecular weight distribution and a uniform composition distribution of a comonomer according to a single active point characteristic. In addition, it is possible to change the stereoregularity, copolymerization properties, molecular weight, crystallinity, and the like of the polymer according to the modification of the ligand structure of the catalyst and the change of polymerization conditions.

In particular, in the case of various commercialized polypropylenes, products with Ziegler-Natta catalysts are the mainstream, as they seek to reduce the occurrence of volatile organic compounds (VOC) in many product groups due to the recent change in environmental awareness. As an eco-friendly material such as, etc., the conversion to a polypropylene resin product with a metallocene catalyst having low odor and low dissolution characteristics is being accelerated.

However, in the case of producing polypropylene using a metallocene catalyst known so far, there is a limit to increasing the content of ethylene, which is a comonomer, because the melting point is lower than that of the Ziegler Natta catalyst. It is difficult to implement low and high transparency.

Accordingly, there is a need to develop a method for producing highly transparent polypropylene useful for injection products by maximizing ethylene content as well as low total volatile organic compound emission (TVOC) using a metallocene catalyst.

The present specification is to provide a high transparency injection propylene-ethylene random copolymer using a low total volatile organic compound emission (TVOC) and a high comonomer content.

In the present invention, the melting point (Tm) is 125 ℃ or more, the content of ethylene is 4.0% by weight or more, the crystallization temperature (Tc) is 75 ℃ or less, the melt index (MI _2.16 , 230 ℃, measured at a load of 2.16 kg) A melt index) of 16 g/min to 22 g/min provides a propylene-ethylene random copolymer.

The propylene-ethylene random copolymer may have a melting point (Tm) of 125°C to 150°C, an ethylene content of 4.0% to 5.5% by weight, and a crystallization temperature (Tc) of 65°C to 75°C. I can.

In addition, the propylene-ethylene random copolymer may have a xylene soluble content (X.S, Xylene soluble) of 1.0% by weight or less.

In addition, the propylene-ethylene random copolymer may have a haze of 7.5% or less measured according to the ASTM 1003 method, and a total volatile organic compound emission (TVOC) measured according to the VDA 277 method may be 70 ppm or less. .

Meanwhile, the propylene-ethylene random copolymer may be prepared by copolymerizing a propylene monomer and an ethylene comonomer in the presence of a catalyst composition including a metallocene compound of Formula 1 below.

[Formula 1]

In Formula 1,

M is a Group 4 transition metal,

X ¹ and X ² are the same as or different from each other, and each independently a halogen element,

R ¹ and R ² are the same as or different from each other, and each independently C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkoxyalkyl, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 arylalkyl,

R ³ to R ⁶ are the same as or different from each other, and each independently C _1-20 alkyl,

R ⁷ is substituted or unsubstituted C _6-20 aryl,

R ⁸ is C _1-20 alkyl.

At this time, in Formula 1, R ¹ and R ² may each be C _1-8 straight or branched chain alkyl, or C _2-12 straight or branched alkoxyalkyl, specifically methyl, ethyl, propyl, isopropyl , Butyl, isobutyl, t-butyl, hexyl, or t-butoxyhexyl.

And, in Formula 1, R ³ to R ⁶ may each be C _1-6 straight or branched chain alkyl or C _1-3 straight or branched chain alkyl, specifically methyl, ethyl, propyl, or isopropyl, iso It may be propyl, preferably methyl.

In addition, in Formula 1, M may be preferably zirconium (Zr) or hafnium (Hf).

And, in Formula 1, R ⁷ may be phenyl, C _1-6 linear or branched alkyl substituted phenyl, naphthyl, or C _1-6 linear or branched alkyl substituted naphthyl, specifically The phenyl or naphthyl may be one in which one or two or more of the hydrogen substituents are each substituted with C _1-6 straight or branched chain alkyl. For example, the phenyl or naphthyl may be one in which one or two or more of the hydrogen substituents are each substituted with methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl.

And, in Formula 1, R ⁸ may be C _1-6 straight or branched chain alkyl or C _1-3 straight or branched chain alkyl, specifically methyl, ethyl, or propyl, preferably methyl. I can.

In addition, the metallocene compound represented by Formula 1 may be specifically represented by Formula 1-1 below.

[Formula 1-1]

In Formula 1-1, M, X ¹ , X ² , R ¹ , R ² , R ⁷ are as defined in Formula 1.

In addition, the metallocene compound represented by Chemical Formula 1 may be, for example, any one of compounds represented by the following structural formula. The following structural formula is only an example for explaining the present invention, but the present invention is not limited thereto.

.

.

The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention.

Singular expressions include plural expressions unless the context clearly indicates otherwise.

In the present specification, terms such as "comprise", "include" or "have" are used to describe implemented features, numbers, steps, components, or combinations thereof, and one or more other features, numbers, and steps , Components, combinations or additions thereof are not excluded.

In addition, in the present specification, when each layer or element is referred to as being formed “on” or “on” each layer or element, it means that each layer or element is formed directly on each layer or element, or It means that a layer or element may be additionally formed between each layer, on the object, or on the substrate.

The present invention will be described in detail below and exemplify specific embodiments, as various changes can be made and various forms can be obtained. However, this is not to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in detail.

The propylene-ethylene random copolymer according to an embodiment of the present invention has a melting point (Tm) of 125°C or higher, an ethylene content of 4.0% by weight or more, a crystallization temperature (Tc) of 75°C or less, and a melt index ( It is characterized in that it satisfies the condition that the melt index measured at MI _2.16 , 230° C., and 2.16 kg load) is 16 g/min to 22 g/min.

The propylene (co)polymer prepared with the Ziegler-Natta catalyst has a problem in that the stiffness is greatly reduced due to the decrease in crystal properties, and the volatile organic compound emission amount (VOC) is high. In addition, even when using an existing metallocene catalyst, the melting point is low, fouling occurs in the polymerization process, and there is a limit to increasing the content of ethylene, which is a comonomer, so that the ethylene content is increased to maintain high transparency and injection There is a need to improve workability to be suitable for molding.

Accordingly, according to the present invention, it is possible to provide a high transparency injection-use propylene-ethylene random copolymer having low total volatile organic compound emission (TVOC) and excellent workability with high rigidity.

In particular, the present invention provides a propylene-ethylene random copolymer containing ethylene as a comonomer among randomly copolymerized polypropylene, a random copolymer using butene instead of ethylene as a comonomer or additionally using butene with ethylene. In the case of the terpolymer, the haze value is not good, so it is difficult to apply it as a highly transparent injection resin such as the present invention.

The propylene-ethylene random copolymer according to an embodiment of the present invention is characterized in that the content of ethylene is 4.0% by weight or more at a melting point (Tm) of 120° C. or higher. In particular, the propylene-ethylene random copolymer can secure a very high melting point in the resin of homopolypropylene and realize high copolymerization with ethylene by using a metallocene catalyst of a novel structure as described below, and thus high ethylene It can be said that it maintains a high melting point even in the content.

Specifically, the propylene-ethylene random copolymer according to an embodiment of the present invention may have a melting point (Tm) of 125°C or higher or 125°C to 150°C. By having such a high melting point, not only does not cause fouling in the polymerization process, but also exhibits excellent processability and heat resistance. More specifically, the propylene-ethylene random copolymer may have a melting point (Tm) of 125.1 °C or higher or 125.1 °C to 150 °C.

In addition, the propylene-ethylene random copolymer may have a crystallization temperature (Tc) of 75 °C or less or 65 °C to 75 °C. By having such a low crystallinity temperature, the crystallinity is lowered, and when applied to injection products such as films, it has a low haze value and high transparency can be secured. More specifically, the propylene-ethylene random copolymer may have a crystallization temperature (Tc) of 74.5°C or less or 65°C to 74.5°C, or 74°C or less or 68°C to 74°C, or 74°C or less or 70°C to 73.8°C. have.

In the present invention, the melting point (Tm) and the crystallization temperature (Tc) can be measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, after heating the polypropylene polymer to 200 °C by increasing the temperature, it was maintained at that temperature for 5 minutes, then lowered to 30 °C, and the temperature was increased again to obtain a DSC (Differential Scanning Calorimeter, manufactured by TA) curve. The temperature corresponding to the top is the melting point (Tm). Thereafter, when the temperature is again lowered to 30° C., the top of the curve is taken as the crystallization temperature (Tc). At this time, the rate of rise and fall of the temperature is 10 °C/min, and the melting point (Tm) and crystallization temperature (Tc) are measured in a section where the second temperature rises and falls.

In addition, the propylene-ethylene random copolymer according to an embodiment of the present invention may have an ethylene content of 4.0 wt% or more or 4.0 wt% to 5.5 wt% at a melting point (Tm) of 125° C. or higher as described above. As such, it maintains a high melting point and increases the ethylene content, so that when applied to injection products such as films, it has a low haze value and high transparency can be secured. More specifically, the propylene-ethylene random copolymer may have an ethylene content of 4.1 wt% or more, 4.1 wt% to 5.5 wt%, or 4.2 wt% or more, or 4.2 wt% to 5.5 wt%.

In the case of producing a propylene-ethylene random copolymer using a conventional comonomer, a different comonomer enters between the main chains and deforms the lamella structure of the resin, thereby lowering the melting point (Tm) and balancing the stiffness and impact strength (valancing). ) Was not maintained or there was a problem that it was difficult to secure process stability. On the other hand, in the present invention, by using a metallocene catalyst of a novel structure as described later, it is possible to secure a very high melting point in the resin of homopolypropylene and to realize high copolymerization with ethylene. It can exhibit improved physical properties that maintain the melting point.

In the present invention, the content of ethylene, which is a comonomer in the propylene-ethylene random copolymer, is according to ASTM D 5576 of the American Society for Testing and Materials, and the film or film-type specimen of the propylene-ethylene random copolymer is used as a magnetic holder of the FT-IR equipment. After fixing at, the height of the peak of 4800 cm ^-1 to 3500 cm ^-1 reflecting the specimen thickness in the IR absorption spectrum and the area of 710 cm ^-1 to 760 cm ^-1 in which the ethylene component appears, respectively, were measured, and the measured values The comonomer content is calculated by substituting the value obtained by dividing the area of the 710 cm ^-1 to 760 cm ^-1 peak of the standard sample by the peak height of 4800 cm ^-1 to 3500 cm ^-1 to the calibration equation obtained by plotting Can be calculated.

On the other hand, the propylene-ethylene random copolymer according to an embodiment of the present invention has a melt index (MI _2.16 ) of about 16 g/10min as measured with a load of 2.16 kg at 230°C according to ASTM D 1238 of the American Society for Testing and Materials. It is about 22 g/10min. By optimizing the range of the melt index in this way, it is possible to obtain a high-transparent product while maintaining excellent processability at the time of jux molding. More specifically, the propylene-ethylene random copolymer may have a melt index (MI _2.16 ) of about 17 g/10min to about 21 g/10min or about 18 g/10min to about 20 g/10min. In particular, when the melt index (MI _2.16 ) of the propylene-ethylene random copolymer is less than about 16 g/10min, the processability is poor and the injection pressure increases, so that injection cannot be performed, and when it exceeds about 22 g/10min, the viscosity is Because it falls off and cannot be injected, it cannot be used as an injection resin.

As described above, the propylene-ethylene random copolymer of the present invention maintains a high ethylene content of 4.0% by weight or more with a melting point (Tm) of 125° C. or higher, unlike the conventional Ziegler-Natta catalyst applied polypropylene or the conventional metallocene catalyst applied polypropylene. And, by optimizing a low crystallinity temperature (Tc) of 75 ℃ or less and a melt index (MI _2.16 , 230 ℃, melt index measured at 2.16 kg load) from 16 to 22 g/min, excellent in polymerization process and injection molding While securing processability, total volatile organic compound emission (TVOC) is low, and high stiffness and high transparency can be exhibited.

As an example, the propylene-ethylene random copolymer according to an embodiment of the present invention may have a xylene soluble component (XS, Xylene soluble) of about 1.0% by weight or less, or about 0.85% by weight or less, or about 0.7% by weight or less. have. This low xylene dissolution is a value indicating the content of the atactic component in the entire copolymer, and the lower the content, the lower the degree of sticky of the propylene-ethylene random copolymer. This is an advantage that can be secured in polymerization using a metallocene catalyst. The propylene-ethylene random copolymer according to the present invention has an extremely low probability of causing process defects during processing and heat sealing due to a low content of xylene dissolved matter.

In addition, the propylene-ethylene random copolymer may exhibit high transparency as a haze of about 7.5% or less, or about 7.3% or less, or about 7.2% or less, as measured according to ASTM 1003 method of the American Society for Testing and Materials.

In addition, the propylene-ethylene random copolymer may have a total volatile organic compound emission amount (TVOC) of about 70 ppm or less, or about 65 ppm or less, or about 60 ppm or less, as measured according to the VDA 277 method. By having such a low total volatile organic compound emission (TVOC), it is possible to secure eco-friendliness with a propylene-ethylene random copolymer for transparent injection used as a food container.

As described above, the propylene-ethylene random copolymer of the present invention can secure high rigidity and excellent transparency, as well as superior process stability and processability than conventional Ziegler-Natta catalyst applied polypropylene or conventional metallocene catalyst applied polypropylene.

The propylene random copolymer according to an embodiment of the present invention having the above physical properties and constitutional characteristics is a propylene monomer and an ethylene comonomer in the presence of a catalyst composition comprising a metallocene compound of Formula 1 as a catalytic active component. It can be prepared by a manufacturing method comprising the step of randomly copolymerizing.

[Formula 1]

In Formula 1,

M is a Group 4 transition metal,

X ¹ and X ² are the same as or different from each other, and each independently a halogen element,

R ¹ and R ² are the same as or different from each other, and each independently C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkoxyalkyl, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 arylalkyl,

R ³ to R ⁶ are the same as or different from each other, and each independently C _1-20 alkyl,

R ⁷ is substituted or unsubstituted C _6-20 aryl,

R ⁸ is C _1-20 alkyl.

Meanwhile, in the present specification, the following terms may be defined as follows unless there is a specific limitation.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

Alkyl having 1 to 20 carbon atoms (C _1-20 ) may be linear, branched or cyclic alkyl. Specifically, the alkyl having 1 to 20 carbon atoms is a linear alkyl having 1 to 20 carbon atoms; Straight chain alkyl having 1 to 15 carbon atoms; Straight chain alkyl having 1 to 5 carbon atoms; Branched or cyclic alkyl having 3 to 20 carbon atoms; Branched or cyclic alkyl having 3 to 15 carbon atoms; Or it may be a branched chain or cyclic alkyl having 3 to 10 carbon atoms. For example, the alkyl having 1 to 20 carbon atoms (C _1-20 ) is methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl , Cyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

Alkenyl having 2 to 20 carbon atoms (C _2-20 ) includes linear or branched alkenyl, and specifically allyl, allyl, ethenyl, propenyl, butenyl, pentenyl, etc. It is not limited only.

Examples of alkoxy having 1 to 20 carbon atoms (C _1-20 ) include methoxy group, ethoxy, isopropoxy, n-butoxy, tert-butoxy, phenyloxy, and cyclohexyloxy groups, but are limited thereto. It does not become.

The alkoxyalkyl group having 2 to 20 carbon atoms (C _2-20 ) is a functional group in which at least one hydrogen of the above-described alkyl is substituted with alkoxy, specifically methoxymethyl, methoxyethyl, ethoxymethyl, iso-propoxymethyl, alkoxyalkyl such as iso-propoxyethyl, iso-propoxypropyl, iso-propoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxypropyl, and tert-butoxyhexyl; Or aryloxyalkyl such as phenoxyhexyl, but is not limited thereto.

Alkylsilyl having 1 to 20 (C _1-20 ) carbon atoms or alkoxysilyl group having 1 to 20 carbon atoms (C _1-20 ) is substituted with 1 to 3 hydrogens of -SiH ₃ as alkyl or alkoxy as described above. It is a substituted functional group, specifically, alkylsilyl, such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl group, or dimethylpropylsilyl; Alkoxysilyl such as methoxysilyl, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl; Alkoxyalkylsilyl such as methoxydimethylsilyl, diethoxymethylsilyl, or dimethoxypropylsilyl may be mentioned, but the present invention is not limited thereto.

Silylalkyl having 1 to 20 carbon atoms (C _1-20 ) is a functional group in which one or more hydrogens of alkyl as described above are substituted with silyl, specifically -CH ₂ -SiH ₃ , methylsilylmethyl or dimethylethoxysilylpropyl, etc. However, it is not limited thereto.

In addition, the alkylene having 1 to 20 carbon atoms (C _1-20 ) is the same as the above-described alkyl, except that it is a divalent substituent, specifically methylene, ethylene, propylene, butylene, pentylene, hexylene, hep Styrene, octylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and the like, but are not limited thereto.

The aryl having 6 to 20 carbon atoms (C _6-20 ) may be a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. As an example, the aryl having 6 to 20 carbon atoms (C _6-20 ) may include phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, etc., but is not limited thereto.

_Alkylaryl having 7 to 20 carbon atoms (C _7-20 ) may mean a substituent in which at least one hydrogen of the hydrogen of the aromatic ring is substituted by the above-described alkyl. As an example, the alkylaryl having 7 to 20 carbon atoms (C _7-20 ) may include methylphenyl, ethylphenyl, methylbiphenyl, methylnaphthyl, etc., but is not limited thereto.

The arylalkyl having 7 to 20 carbon atoms (C _7-20 ) may mean a substituent in which at least one hydrogen of the above-described alkyl is substituted by the above-described aryl. For example, the arylalkyl having 7 to 20 carbon atoms (C _7-20 ) may include phenylmethyl, phenylethyl, biphenylmethyl, naphthylmethyl, and the like, but is not limited thereto.

In addition, the arylene having 6 to 20 carbon atoms (C _6-20 ) is the same as the aryl described above, except that it is a divalent substituent, and specifically, phenylene, biphenylene, naphthylene, anthracenylene, phenanthrenylene , Fluorenylene, and the like, but are not limited thereto.

In addition, the Group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf), or rutherfordium (Rf), and specifically titanium (Ti), zirconium (Zr), or hafnium (Hf) It may be, and more specifically, zirconium (Zr) or hafnium (Hf), but is not limited thereto.

In addition, the Group 13 element may be boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), and specifically boron (B) or aluminum (Al). There is, but is not limited to this.

The above-described substituents are optionally a hydroxy group within a range exhibiting the same or similar effect as the desired effect; halogen; Alkyl or alkenyl, aryl, alkoxy; Alkyl or alkenyl, aryl, alkoxy containing at least one hetero atom among the heteroatoms of groups 14 to 16; Silyl; Alkylsilyl or alkoxysilyl; Phosphine group; Phosphide group; Sulfonate group; And it may be substituted with one or more substituents selected from the group consisting of a sulfone group.

The catalyst composition used for preparing the propylene-ethylene random copolymer according to an embodiment of the present invention includes the compound of Formula 1 as a single metallocene catalyst. Accordingly, it can be seen that the molecular weight distribution can be significantly narrowed compared to the conventional propylene copolymer prepared by mixing two or more types of catalysts, and accordingly, the rigidity of the propylene-ethylene random copolymer is improved.

The metallocene compound represented by Chemical Formula 1 has an asymmetric structure in which different cyclopentadienyl-based groups are connected to each other by a bridge as a ligand.

Specifically, in Chemical Formula 1, a cyclopentadienyl group substituted with an alkyl group is connected to the bridge at the upper side of the ligand, and in Chemical Formula 1, an indacenyl structure having a specific substituent is connected to the bridge at the lower side of the ligand. Connected.

Depending on the unique structure as described above, since the two cyclopentadienyl different from each other may have various characteristics or take optional advantages, it may exhibit more excellent catalytic activity.

Specifically, in the cyclopentadienyl structure, a hydrogen functional group is substituted with an alkyl group, so that when forming polypropylene, a certain steric spatial arrangement (steric) can be maintained to secure isotacticity and high activity can be maintained. have. In the case of cyclopentadienyl (Cp) substituted with only hydrogen, since there is no bulky part, the catalyst faces completely open when propylene is inserted, so the tacticity collapses, resulting in atactic polypropylene. PP).

In addition, when propylene (C3) and H ₂ are reacted together, a competitive reaction occurs. If a bulky structure is substituted at position 2 of the indacenyl structure in the ligand of Formula 1, for example, When R ⁸ is substituted with C _1-20 alkyl, a certain steric spatial arrangement is given to the metal center, so that the reactivity of H ₂ , which has a smaller size compared to C3, is improved. Therefore, when a structure in which R ⁸ is substituted with C _1-20 alkyl in the form of methyl or the like at position 2 of the indacenyl structure is bonded, hydrogen reactivity may be increased in the polymerization process.

In addition, by including an aryl substituent that can enrich electrons at position 4 of the indacenyl structure, for example, R ⁷ is substituted or unsubstituted C _6-20 aryl substituent, the bridge of Formula 1 It is possible to secure a higher catalytic activity by giving electrons to a metal atom included in the structure in abundance.

In particular, in the case of the indacenyl structure of the metallocene compound represented by Formula 1, a very excellent effect can be obtained in the active portion of the combination with cyclopentadienyl than the general indenyl structure. This can secure a flat structure in which the indacenyl structure faces more than indenyl in the steric effect of cyclopentadienyl, and has a certain effect on the active site, thereby affecting the activation of propylene monomers. It seems to work very favorably. This result can be confirmed by an increase in the tacticity of the polymerized polypropylene.

As described above, the metallocene compound represented by Chemical Formula 1 is in a form in which two ligands are connected by a bridge group and supplies electrons to the transition metal, so that it can have high structural stability, and a carrier It can exhibit high polymerization activity even when supported on.

In this case, in Formula 1, M may be preferably zirconium (Zr) or hafnium (Hf).

And, in Formula 1, R ¹ and R ² may each be C _1-8 straight or branched chain alkyl, or C _2-12 straight or branched alkoxyalkyl, specifically methyl, ethyl, propyl, isopropyl, It may be butyl, isobutyl, t-butyl, hexyl, or t-butoxyhexyl.

And, in Formula 1, R ³ to R ⁶ may each be C _1-6 straight or branched chain alkyl or C _1-3 straight or branched chain alkyl, specifically methyl, ethyl, propyl, or isopropyl, iso It may be propyl, preferably methyl.

And, in Formula 1, R ⁷ may be phenyl, C _1-6 linear or branched alkyl substituted phenyl, naphthyl, or C _1-6 linear or branched alkyl substituted naphthyl, specifically The phenyl or naphthyl may be one in which one or two or more of the hydrogen substituents are each substituted with C _1-6 straight or branched chain alkyl. For example, the phenyl or naphthyl may be one in which one or two or more of the hydrogen substituents are each substituted with methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl.

Substituents at each position of these aromatic groups can supply sufficient electrons to the aromatic group by an inductive effect, and by increasing the total size of the metallocene compound and increasing the usable angle, it is easy to access the monomer. Thus, it is possible to exhibit more excellent catalytic activity.

And, in Formula 1, R ⁸ may be C _1-6 straight or branched chain alkyl or C _1-3 straight or branched chain alkyl, specifically methyl, ethyl, or propyl, preferably methyl. I can.

In addition, the metallocene compound represented by Formula 1 may be specifically represented by Formula 1-1 below.

[Formula 1-1]

In Formula 1-1, M, X ¹ , X ² , R ¹ , R ² , R ⁷ are as defined in Formula 1.

In addition, the compound represented by Formula 1 may be any one of compounds represented by the following structural formula, for example.

.

.

The metallocene compound represented by Formula 1 can be prepared by a method for synthesizing known organic compounds, and is described in more detail in Examples to be described later.

Meanwhile, in the method of preparing the metallocene compound or catalyst composition of the present invention, the equivalent (eq) means a molar equivalent (eq/mol).

The metallocene catalyst used in the present invention may be used in the form of a supported metallocene catalyst by supporting the metallocene compound represented by Formula 1 on a carrier together with a cocatalyst compound.

In the supported metallocene catalyst according to the present invention, as an organometallic compound including a Group 13 metal, as a cocatalyst supported together on a support to activate the metallocene compound, olefin is polymerized under a general metallocene catalyst. It is not particularly limited as long as it can be used.

Specifically, the cocatalyst compound may include one or more aluminum-containing cocatalysts of the following formula (2).

[Formula 2]

-[Al(R ²² )-O] _m-

In Formula 2, R ²² are the same as or different from each other, and each independently halogen, C _1-20 alkyl or C _1-20 haloalkyl; m is an integer of 2 or more.

The polymerization activity can be further improved by the use of such a cocatalyst.

As an example, the cocatalyst of Formula 2 may be an alkylaluminoxane-based compound in which a repeating unit is bonded in a linear, circular or network type, and specific examples of such a cocatalyst include methylaluminoxane (MAO), ethylaluminoxane And isobutyl aluminoxane or butyl aluminoxane.

In the supported metallocene catalyst according to the present invention, the mass ratio of the total transition metal to the carrier contained in the metallocene compound represented by Formula 1 may be 1:10 to 1:1000. When the carrier and the metallocene compound are included in the mass ratio, the optimum shape may be exhibited. In addition, the mass ratio of the cocatalyst compound to the carrier may be 1:1 to 1:100.

In the supported metallocene catalyst according to the present invention, a carrier containing a hydroxy group on the surface may be used as the carrier, and preferably has a highly reactive hydroxy group and a siloxane group from which moisture is removed from the surface. Any carrier can be used.

For example, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are usually oxides, carbonates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) ₂ , It may contain sulfate and nitrate components.

The drying temperature of the carrier is preferably 200°C to 800°C, more preferably 300°C to 600°C, and most preferably 300°C to 400°C. When the drying temperature of the carrier is less than 200°C, there is too much moisture to react with the surface moisture and the cocatalyst, and when it exceeds 800°C, the pores on the surface of the carrier are combined and the surface area decreases, and there are many hydroxyl groups on the surface. It is not preferable because it disappears and only siloxane groups remain, and the reaction site with the cocatalyst decreases.

The amount of hydroxy group on the surface of the carrier is preferably 0.1 mmol/g to 10 mmol/g, and more preferably 0.5 mmol/g to 5 mmol/g. The amount of hydroxy groups on the surface of the carrier can be controlled by a method and conditions for preparing the carrier or drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than 0.1 mmol/g, the reaction site with the cocatalyst is small, and if it exceeds 10 mmol/g, it is not preferable because it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. not.

Meanwhile, the propylene-ethylene random copolymer according to the present invention can be prepared by copolymerizing a monomer and a comonomer in the presence of the metallocene catalyst described above.

The polymerization reaction may be carried out by copolymerization by contacting a propylene monomer and a comonomer using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

In addition, the polymerization temperature may be about 25 °C to about 500 °C, preferably about 25 °C to about 200 °C, more preferably about 50 °C to about 100 °C. In addition, the polymerization pressure may be about 1 kgf/cm 2 to about 100 kgf/cm 2, preferably about 1 kgf/cm 2 to about 50 kgf/cm 2, more preferably about 10 kgf/cm 2 to about 40 kgf/cm 2 .

In addition, the polymerization reaction may be carried out in the presence of hydrogen gas, and specifically, hydrogen gas of about 350 ppm or less or about 0 to about 350 ppm, or about 300 ppm or less or about 0 ppm to about 300 ppm based on the propylene monomer content , Or about 250 ppm or less, or about 0 ppm to about 250 ppm, or about 200 ppm or less, or about 0 ppm to about 200 ppm. For example, depending on the metallocene compound of the supported catalyst, the hydrogen input amount is at least 50 ppm or more, or 100 ppm or more, or about 100 ppm or more, or 120 ppm or more, or 150 ppm or more in the above-described range. The polymerization reaction can be carried out.

The supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof, and an aromatic hydrocarbon solvent such as toluene and benzene, and dichloromethane and chlorobenzene. It can be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom and injected. The solvent used here is preferably used after removing a small amount of water or air, which acts as a catalyst poison, by treating a small amount of alkyl aluminum, and it is possible to further use a cocatalyst.

As described above, the propylene-ethylene random copolymer according to the present invention may be prepared by copolymerizing propylene and ethylene using the above-described supported metallocene catalyst. As a result, the propylene-ethylene random copolymer maintains a high melting point even with an increased ethylene content, has a low crystallization temperature and an appropriate melting index, and thus has excellent process stability, processability and extrusion properties, and has high rigidity. Since a low total volatile organic compound emission (TVOC) and high transparency can be realized, the propylene-ethylene random copolymer according to the present invention is an eco-friendly material and can be preferably applied to products for high-transparent thin film injection.

Propylene-ethylene random copolymer according to the present invention. It maintains a high melting point, ensures excellent physical properties such as stiffness and impact strength, and process stability that does not cause fouling, while also realizing excellent processability, which is particularly easy for injection molding, while maintaining a high level of ethylene content as a comonomer. It is advantageous in manufacturing highly transparent injection products used as eco-friendly materials, such as food containers, because it can increase the crystallinity by increasing it to a lower level of crystallinity, and has a significantly lower total volatile organic compound emission (TVOC).

Hereinafter, the functions and effects of the invention will be described in more detail through specific embodiments of the invention. However, these embodiments are only presented as examples of the invention, and the scope of the invention is not determined thereby.

<Example>

<Preparation of metallocene compound>

Synthesis Example 1

Preparation of ligand compound (2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl) dimethyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro dimethyl silane (1.05 eq) was added at -10°C, followed by stirring at room temperature overnight. In another reactor, add 2-methyl-4-(3',5'-di(tert-butyl)phenyl) indacene (2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) to toluene. After dissolving in a mixed solvent (volume ratio of 3/2, 0.5 M) of /tetrahydrofuran (Toluene/THF), n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Dimethylsilanediyl(2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in toluene/diethylether (Toluene/Ether, volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by 5 at room temperature. Stir for hours. A slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

For the thus obtained transition metal compound, NMR data were measured with Bruker AVANCE III HD 500 MHz NMR/PABBO (1H/19F/Broad band) probe: 1H, solvent: CDCl ₃ .

¹ H-NMR (500 MHz, CDCl ₃ ): 7.73 (s, 2H), 7.56 (s, 1H), 7.42 (s, 1H), 6.36 (s, 1H), 2.85-2.80 (m, 4H), 2.12 (s, 6H), 1.95 (m, 2H), 1.79 (s, 9H), 1.31 (s, 18H), 1.00 (s, 6H) ppm

Synthesis Example 2

Preparation of ligand compound (2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl) dimethyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro dimethyl silane (1.05 eq) was added at -10°C, followed by stirring at room temperature overnight. In another reactor, add 2-methyl-4-(3',5'-di(tert-butyl)phenyl) indacene (2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) to toluene. After dissolving in a mixed solvent (volume ratio of 3/2, 0.5 M) of /tetrahydrofuran (Toluene/THF), n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Dimethylsilanediyl(2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl)(2,3,4,5-tetramethyl cyclopentadienyl) hafnium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing HfCl ₄ (1 eq) in toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.78 (s, 2H), 7.6 (s, 1H), 7.46 (s, 1H), 6.41 (s, 1H), 2.98-2.92 (m, 4H), 2.14 (s, 6H), 1.98 (m, 2H), 1.83 (s, 6H), 1.8 (s, 3H), 1.33 (s, 18H), 1.28 (s, 6H) ppm

Synthesis Example 3

Preparation of ligand compound (2-Methyl-4-(4'-tertbutylphenyl)Indacenyl) dimethyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro dimethyl silane (1.05 eq) was added at -10°C, followed by stirring at room temperature overnight. In another reactor, 2-methyl-4-(4-(tert-butyl)phenyl) indacene (2-Methyl-4-(4'-tertbutylphenyl) Indacene (1 eq)) was added to toluene/tetrahydrofuran (Toluene/THF). ) Was dissolved in a mixed solvent (volume ratio of 3/2, 0.5 M), and then n-BuLi (1.05 eq) was slowly added dropwise at -25° C., followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Dimethylsilanediyl(2-Methyl-4-(4'-tertbutylphenyl)Indacenyl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.42 (s, 1H), 7.38 (d, 2H), 7.30 (d, 2H), 6.37 (s, 1H), 2.85-2.79 (m, 4H), 2.12 (s, 6H), 1.94 (m, 2H), 1.79 (s, 9H), 1.30 (s, 9H), 1.00 (s, 6H) ppm

Synthesis Example 4

Preparation of ligand compound (2-Methyl-4-phenylIndacenyl) dimethyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro dimethyl silane (1.05 eq) was added at -10°C, followed by stirring at room temperature overnight. In another reactor, 2-methyl-4-phenyl) indacene (1 eq)) was added to a mixed solvent of toluene/tetrahydrofuran (Toluene/THF) (volume ratio 3/2, 0.5 M ), n-BuLi (1.05 eq) was slowly added dropwise at -25 °C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Dimethylsilanediyl (2-Methyl-4-phenylIndacenyl) (2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.54-7.38 (m, 6H), 6.37 (s, 1H), 2.85-2.80 (m, 4H), 2.12 (s, 6H), 1.95 (m, 2H) , 1.79 (s, 9H), 0.99 (s, 6H) ppm

Synthesis Example 5

Preparation of ligand compound (2-Methyl-4-(2'-naphthylene) Indacenyl) dimethyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro dimethyl silane (1.05 eq) was added at -10°C, followed by stirring at room temperature overnight. Mixing of toluene/tetrahydrofuran (Toluene/THF) with 2-methyl-4-(2'-naphthylene) indacene (1 eq)) in another reactor After dissolving in a solvent (volume ratio 3/2, 0.5 M), n-BuLi (1.05 eq) was slowly added dropwise at -25 °C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Dimethylsilanediyl(2-Methyl-4-(2'-naphthylene)Indacenyl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 8.80 (d, 1H), 8.50 (d, 1H), 8.2-8.05 (m, 2H), 7.75 (t, 1H), 7.55-7.36 (m, 3H) , 6.36 (s, 1H), 2.85-2.81 (m, 4H), 2.13 (s, 6H), 1.95 (m, 2H), 1.8 (s, 6H), 1.78 (s, 3H), 1.01 (s, 6H) ) ppm

Synthesis Example 6

Preparation of ligand compound (2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl) diethyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro diethyl silane (1.05 eq) was added at -10°C, followed by stirring at room temperature overnight. Toluene 2-Methyl-4-(3',5'-di(tert-butyl)phenyl) indacene (2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) in another reactor After dissolving in a mixed solvent (volume ratio of 3/2, 0.5 M) of /tetrahydrofuran (Toluene/THF), n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Diethylsilanediyl(2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.73 (s, 2H), 7.55 (s, 1H), 7.41 (s, 1H), 6.38 (s, 1H), 2.86-2.80 (m, 4H), 2.12 (s, 6H), 1.95 (m, 2H), 1.79 (s, 9H), 1.28 (t, 6H), 0.94 (m, 4H) ppm

Synthesis Example 7

Preparation of ligand compound (2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl) dihexyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro dihexyl silane (1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. Toluene 2-Methyl-4-(3',5'-di(tert-butyl)phenyl) indacene (2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) in another reactor After dissolving in a mixed solvent (volume ratio of 3/2, 0.5 M) of /tetrahydrofuran (Toluene/THF), n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Dihexylsilanediyl(2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.74 (s, 2H), 7.56 (s, 1H), 7.43 (s, 1H), 6.36 (s, 1H), 2.85-2.80 (m, 4H), 2.12 (s, 6H), 1.95 (m, 2H), 1.80 (s, 6H), 1.79 (s, 3H), 1.38-1.28 (m, 34H), 0.88 (t, 6H), 0.68 (m, 4H) ppm

Synthesis Example 8

Preparation of ligand compound (2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl) methylpropyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro methylpropyl silane (1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. Toluene 2-Methyl-4-(3',5'-di(tert-butyl)phenyl) indacene (2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) in another reactor After dissolving in a mixed solvent (volume ratio of 3/2, 0.5 M) of /tetrahydrofuran (Toluene/THF), n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Methylpropylsilanediyl(2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.73 (s, 2H), 7.55 (s, 1H), 7.42 (s, 1H), 6.36 (s, 1H), 2.85-2.80 (m, 4H), 2.13 (s, 6H), 1.95 (m, 2H), 1.79 (s, 9H), 1.31 (s, 18H), 1.00-0.84 (m, 10H) ppm

Synthesis Example 9

Preparation of ligand compound (2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl) methylphenyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro methylphenyl silane (1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. Toluene 2-Methyl-4-(3',5'-di(tert-butyl)phenyl) indacene (2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) in another reactor After dissolving in a mixed solvent (volume ratio of 3/2, 0.5 M) of /tetrahydrofuran (Toluene/THF), n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Methylphenylsilanediyl(2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.73 (s, 2H), 7.56 (s, 1H), 7.42-7.28 (m, 6H), 6.38 (s, 1H), 2.88-2.82 (m, 4H) , 2.12 (s, 6H), 1.95 (m, 2H), 1.79 (s, 9H), 1.31 (s, 18H), 0.98 (s, 3H) ppm

Synthesis Example 10

Preparation of ligand compound (2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl) methylhexyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro methylhexyl silane (1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. Toluene 2-Methyl-4-(3',5'-di(tert-butyl)phenyl) indacene (2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) in another reactor After dissolving in a mixed solvent (volume ratio of 3/2, 0.5 M) of /tetrahydrofuran (Toluene/THF), n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Methylhexylsilanediyl(2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.74 (s, 2H), 7.55 (s, 1H), 7.41 (s, 1H), 6.35 (s, 1H), 2.85-2.77 (m, 4H), 2.12 (s, 6H), 1.95 (m, 2H), 1.80 (s, 6H), 1.78 (s, 3H), 1.31 (s, 18H), 1.20-0.81 (m, 16H) ppm

Synthesis Example 11

Preparation of ligand compound (2-Methyl-4-(2',5'-dimethylphenyl)Indacenyl) dimethyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro dimethyl silane (1.05 eq) was added at -10°C, followed by stirring at room temperature overnight. In another reactor, 2-methyl-4-(2',5'-dimethylphenyl) indacene (2-Methyl-4-(2',5'-dimethylphenyl) Indacene (1 eq)) was added toluene/tetrahydrofuran ( Toluene/THF) was dissolved in a mixed solvent (volume ratio of 3/2, 0.5 M), and then n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Dimethylsilanediyl(2-Methyl-4-(2',5'-dimethylphenyl)Indacenyl)(2,3,4,5-tetramethyl cyclopentadienyl) hafnium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing HfCl ₄ (1 eq) in toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.76 (s, 1H), 7.54 (s, 1H), 7.35-7.25 (m, 2H), 6.41 (s, 1H), 2.89-2.83 (m, 4H) , 2.48 (s, 3H), 2.3 (s, 3H), 2.18 (s, 6H), 1.98 (m, 2H), 1.83 (s, 6H), 1.84 (s, 3H), 1.25 (s, 6H) ppm

Synthesis Example 12

Preparation of ligand compound (2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl) 6-tertButoxyhexylmethyl (2,3,4,5-tetramethyl cyclopentadienyl) silane

2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) was dissolved in tetrahydrofuran (THF) and then n-butyllithium (n-BuLi, 1.05) at -25 °C. eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro 6- (tert butoxy) hexylmethyl silane (dichloro 6-tertButoxyhexylmethyl silane, 1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. Toluene 2-Methyl-4-(3',5'-di(tert-butyl)phenyl) indacene (2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) in another reactor After dissolving in a mixed solvent (volume ratio of 3/2, 0.5 M) of /tetrahydrofuran (Toluene/THF), n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound 6-tertButoxyhexylmethylsilanediyl(2-Methyl-4-(3',5'-ditertbutylphenyl)Indacenyl)(2,3,4,5-tetramethyl cyclopentadienyl) hafnium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing HfCl ₄ (1 eq) in toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.76 (s, 2H), 7.59 (s, 1H), 7.48 (s, 1H), 6.4 (s, 1H), 3.28 (t, 2H), 2.9-2.83 (m, 4H), 2.15 (s, 6H), 1.96 (m, 2H), 1.82-1.52 (m, 13H), 1.38-1.23 (m, 22H), 1.28 (s, 9H), 0.96-0.86 (m , 5H) ppm

Comparative Synthesis Example 1

Preparation of ligand compound (2-Methyl-4-(4'-tertbutylphenyl)Inden-1yl)dimethyl(2,3,4,5-tetramethyl cyclopentadienyl) silane

After dissolving (2,3,4,5-tetramethyl) cyclopentadiene (1 equiv) in THF (0.3 M), n-BuLi (1.05 eq) was slowly added dropwise at -25 °C, followed by stirring at room temperature for 3 hours. Thereafter, dichloro dimethyl Silane (1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. In another reactor, 2-Methyl-4-(4'-tertbutylphenyl)indene (1 eq) was dissolved in Toluene/THF (3/2, 0.5M), and then n-BuLi (1.05 eq) was slowly added dropwise at -25 °C. Then, it was stirred at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Dimethylsilanediyl(2-Methyl-4-(4'-tertbutylphenyl)Inden-1-yl)(2,3,4,5-tetramethyl cyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) in toluene (1.2 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

Comparative Synthesis Example 2

Preparation of the ligand compound bis(2-Methyl-4-(4'-tertbutylphenyl)Inden-1yl)silane

After dissolving 2-Methyl-4-(4'-tertbutylphenyl)Indene(1 equiv) in Toluene/THF (10:1 0.3 M), n-BuLi (2.1 eq) was slowly added dropwise at -25°C, and then at room temperature. Stir for 3 hours. Then, CuCN (2 mol%) was added and stirred for 30 minutes, dichloro dimethyl Silane (0.53 eq) was added at -10° C., and then stirred at room temperature overnight. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Dimethylsilanediylbis(2-Methyl-4-(4'-tertbutylphenyl)Inden-1yl)zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 10/1, 0.1 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

Comparative Synthesis Example 3

Ligand compound (4-(4'-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacen-7-yl)dimethyl(2-isopropyl-4-(4'-tertbutylphenyl) Preparation of -inden-1-yl) silane

2-isopropyl-4-(4'-tertbutylphenyl)-1-indene (1 equiv) was dissolved in tetrahydrofuran/hexane (THF/Hexane, volume ratio 1/10, 0.3 M), and then n-BuLi ( 1.05 eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. Thereafter, dichloro dimethyl Silane (1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. In another reactor, add 4-(4'-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-7-indacene (1 eq) to Toluene/THF (3/2, 0.5M). After dissolving, n-BuLi (1.05 eq) was slowly added dropwise at -25 °C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Transition metal compound Dimethylsilanediyl(4-(4'-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacen-7-yl)(2-isopropyl-4-(4'-tertbutylphenyl) )-inden-1-yl) Preparation of zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) in toluene (1.2 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

Comparative Synthesis Example 4

Preparation of ligand compound (2-Methyl-4-(4-t-butylphenyl)-tetrahydrocyclopenta[b]naphthalene)dimethyl(2-isopropyl-4-(4'-tert-butylphenyl) silane

Methacrylic chloride (37.5 mL, 375 mmol) was added to AlCl ₃ (100 g, 750 mmol) in well stirred CH ₂ Cl ₂ (600 mL) at -70 °C. After 20 minutes, tetrahydronaphthalene (49.5 g, 375 mmol) was added. The reaction mixture was warmed to room temperature, stirred for 16 hours, and poured into ice water-HCl (1 L/150 mL). The organic layer was separated, and the aqueous layer was extracted with CH ₂ Cl ₂ (2100 mL). The combined organic phases were washed with water, aqueous NaHCO ₃ , dried over MgSO ₄ and evaporated. Vacuum distillation (130-140° C./0.5 Torr) ketone mixture. After storage for 5 days, the desired isomer remains liquid and can be separated by decantation. Yield: 30 g (40%).

2-methyl-2,3,5,6,7,8-hexahydro-1H-cyclopenta[b]naphthalen-1-one (30 g, 150 mmol) in previously prepared CH ₂ Cl ₂ (50 mL) Was added to a suspension of AlCl ₃ (40 g, 300 mmol) in CH ₂ Cl ₂ (250 mL) at -20 °C. After stirring for 20 minutes, Br ₂ (7.7 ml, 150 mmol) was added. The reaction mixture was warmed to room temperature, stirred for 16 hours, and poured into ice water/HCl (500 mL/70 mL). The organic phase was separated, the aqueous phase was extracted with CH ₂ Cl ₂ (twice 50 mL) and the combined organic fractions were washed with water, aqueous KHCO ₃ , dried over MgSO ₄ and evaporated. The residue was distilled in vacuo (175-180 °C/0.5 Torr), and 31 g (74%) of the reaction product, i.e. 2-methyl-2,3,5,6,7,8-hexahydro-1H -Cyclopenta[b]naphthalen-1-one was obtained.

Pd(OAc) ₂ (0.74 g, 3 mol%) and PPh ₃ (1.73 g, 6 mol%) were mixed with the 2-methyl- in well stirred dimethoxyethane (380 ml)/H ₂ O (130 mL). 2,3,5,6,7,8-hexahydro-1H-cyclopenta[b]naphthalen-1-one (31 g, 110 mmol), tert-butylphenylboronic acid (26.7 g, 150 mmol) and Na ₂ CO ₃ (31.8 g, 300 mmol) was added to the mixture. The resulting mixture was refluxed while stirring for 6 hours, cooled, poured into water (700 mL), and extracted with benzene (4 times each 100 mL). The resulting solution was filtered and evaporated. The reaction product, 4-(4-t-butylphenyl)-2-methyl-2,3,5,6,7,8-hexahydro-1H-cyclopenta[b]naphthalen-1-one, was subjected to column chromatography. (Silica gel 60, hexane/CH ₂ Cl ₂ 1:1). The yield was 18.3 g (50%).

LiAIH ₄ (0.95 g, 25 mmol) was added to the 4-(4-tert-butylphenyl)-2-methyl2,3,5,6,7,8-hexahydro-1H- in Et ₂ O (150 mL) To a solution of cyclopenta[b]naphthalen-1-one (16.6 g, 50 mmol) was added at -20°C. The resulting mixture was warmed to room temperature and stirred for an additional hour. Then, 5% HCl (100 mL) was added, and the resulting mixture was extracted with Et ₂ O (3 times each 50 mL). The combined organic phases were washed with water, dried over MgSO ₄ and evaporated. Benzene (300 mL) and p-TSA (0.5 g) were added, and the resulting solution was refluxed within 4 hours with Dean Stark head (controlled by TLC, benzene/EtOAc 4:1). Then, the resulting solution was washed with water, aqueous KHCO ₃ , dried over MgSO ₄ , passed through silica gel and evaporated to give 12.8 g (81%) of the reaction product, i.e. 9-(4-tert- Butylphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene was obtained.

The 9-(4-tert-butylphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene (2.97 g, 9.38 mmol) above in Et ₂ O (50 mL) The solution was cooled to -60 °C and n-BuLi (1.6 M in hexanes, 6.04 mL, 9.67 mmol) was added. The resulting mixture was warmed to room temperature, stirred for 3 hours, cooled to -60° C., and CuCN (50 mg, 0.55 mmol) was added. After 15 minutes, a solution of chloro-(4-(4-tert-butylphenyl)-2-isopropyl-1H-inden-1-yl)-dimethylsilane (9.67 mmol) in Et ₂ O (24 mL) was added. And the resulting mixture was warmed to room temperature and stirred for 16 hours. Water (5 mL) and hexane (200 mL) were added and the organic phase was separated, dried over MgSO ₄ , passed through silica gel and evaporated. The reaction product [4-(4-t-butylphenyl)-2-isopropyl-1H-inden-1-yl][4-(4-tert-butylphenyl)-2-methyl-5,6,7 ,8-tetrahydro-1H-cyclopenta[b]naphthalen-1-yl]dimethylsilane was dried in vacuo and used without purification.

Preparation of transition metal compound Dimethylsilanediyl(2-Methyl-4-(4-t-butylphenyl)-tetrahydrocyclopenta[b]naphthalene)(2-isopropyl-4-(4'-tert-butylphenyl)zirconium dichloride

The ligand compound prepared above, [4-(4-tert-butylphenyl)-2-isopropyl-1H-inden-1-yl][4-(4-tert-butylphenyl)-2-methyl-5, 6,7,8-tetrahydro-1H-cyclopenta[b]naphthalen-1-yl]dimethylsilane (5.82 g, 8.78 mmol) was dissolved in Et ₂ O (60 mL), cooled to -40 °C, n-BuLi (1.6M in hexane, 11.52 mL, 18.44 mmol) was added. The reaction mixture was warmed to room temperature, stirred for 3 hours and evaporated. The residue was suspended in pentane (100 mL), cooled to -60 °C, and ZrCl ₄ (2.15 g, 9.22 mmol) was added. After 5 minutes, Et ₂ O (1 mL) was added. The resulting mixture was warmed to room temperature, stirred for an additional 16 hours, and filtered. The resulting yellowish-orange powder was dried, dimethoxyethane (100 mL) and LiCl (0.3 g) were added, and the mixture was refluxed while stirring for 6 hours. The product was obtained by subsequent recrystallization from dimethoxyethane and CH ₂ Cl ₂ /Et ₂ O. The yield of the rock-form was 0.88 g (24.4%).

Comparative Synthesis Example 5

Preparation of a ligand compound [(6-tertbutoxyhexyl)(methyl)-bis[2-methyl-4-phenyl)-inden-1-yl] silane

First, 100 mL of t-butoxyhexyl magnesium chloride solution (about 0.14 mol, ether) was slowly added dropwise to 100 mL of trichloromethylsilane solution (about 0.21 mol, hexane) over 3 hours at -100°C, It was stirred at room temperature for 3 hours. After separating the transparent organic layer from the mixed solution, the separated transparent organic layer was vacuum-dried to remove excess trichloromethylsilane to obtain a transparent liquid (6-t-butoxyhexyl)dichloromethylsilane.

To 77 mL of 2-methyl-4-phenylindene toluene/THF=10/1 solution (34.9 mmol), 15.4 mL of n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise at 0 °C, and at 80 °C After stirring for 1 hour, the mixture was stirred at room temperature for one day. Thereafter, 5 g of (6-tert-butoxyhexyl)dichloromethylsilane prepared above was slowly added dropwise to the mixed solution at -78°C, and stirred for about 10 minutes, followed by stirring at 80°C for 1 hour. Then, water was added to separate the organic layer, followed by purification on a silica column, followed by vacuum drying to obtain a sticky yellow oil in a yield of 78% (racemic: meso = 1:1).

¹ H NMR (500 MHz, CDCl ₃ ): 0.10 (s, 3H), 0.98 (t, 2H), 1.25 (s, 9H), 1.36~1.50 (m, 8H), 1.62 (m, 8H), 2.26 ( s, 6H), 3.34 (t, 2H), 3.81 (s, 2H), 6.87 (s, 2H), 7.25 (t, 2H), 7.35 (t, 2H), 7.45 (d, 4H), 7.53 (t , 4H), 7.61 (d, 4H)

Preparation of transition metal compound [(6-tertbutoxyhexylmethylsilanediyl)-bis[2-methyl-4-(4'-tertbutylphenyl)]zirconium dichloride

The ligand compound prepared above, (6-tert-butoxyhexyl)(methyl)bis(2-methyl-4-phenyl)indenylsilane ether/hexane=1/1 solution (3.37 mmol) n-butyl in 50 mL 3.0 mL of a lithium solution (2.5 M in hexane) was slowly added dropwise at -78 °C, stirred at room temperature for about 2 hours, and then dried under vacuum. After washing the salt with hexane, it was filtered and dried under vacuum to obtain a yellow solid. Ligand salt and bis (N,N'-diphenyl-1,3-propanediamido) dichlorozirconium bis (tetrahydrofuran) synthesized in a glove box [Zr(C ₅ H ₆ NCH ₂ CH ₂ NC ₅ H ₆ )Cl ₂ (C ₄ H ₈ O) ₂ ] was weighed into a Shrink flask, ether was slowly added dropwise at -78 °C, and then stirred at room temperature for a day. Thereafter, the red reaction solution was separated by filtration, 4 equivalents of an HCl ether solution (1 M) was slowly added dropwise at -78°C, followed by stirring at room temperature for 3 hours. After filtration and vacuum drying, an ansa-metallocene compound as an orange solid component was obtained in a yield of 85% (racemic:meso = 10:1).

¹ H NMR (500 MHz, C ₆ D ₆ , 7.24 ppm): 1.19 (9H, s), 1.32 (3H, s), 1.48-1.86 (10H, m), 2.25 (6H, s), 3.37 (2H, t), 6.95 (2H, s), 7.13 (2H, t), 7.36 (2H, d), 7.43 (6H, t), 7.62 (4H, d), 7.67 (2H, d)

Comparative Synthesis Example 6

Preparation of Ligand Compound (2-Methyl-4-phenyl) Indacen-1-yl)dimethyl(cyclopentadienyl) silane

Dicyclopentadiene was condensed through cracking at 150 °C to extract cyclopentadiene (1 equiv) and dissolved in THF (0.3 M), and then n-BuLi (1.05 eq) was slowly added dropwise at -25 °C, followed by stirring at room temperature for 3 hours. . Thereafter, dichloro dimethyl silane (1.05 eq) was added at -10°C, followed by stirring at room temperature overnight. (2-Methyl-4-phenyl) indacene (1 eq)) to another reactor in a mixed solvent of toluene/tetrahydrofuran (Toluene/THF) (volume ratio 3/2, 0.5 After dissolving in M), n-BuLi (1.05 eq) was slowly added dropwise at -25 °C, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then a mono-Si solution as the first reactant was added. After that, the mixture was stirred at room temperature overnight, worked-up with water, and dried to obtain a ligand.

Preparation of transition metal compound Dimethyl-silanediyl(cyclopentadienyl)(2-methyl-4-phenyl)Indacenyl)zirconium dichloride

The ligand prepared above was dissolved in Toluene/Ether (volume ratio 2/1, 0.53 M), and n-BuLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 5 hours. A slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) in a separate flask was prepared, added to the ligand solution, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was re-introduced to remove LiCl through a filter, etc., the filtrate was vacuum-dried, and dichloromethane/hexane was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title metallocene compound.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.54-7.38 (m, 6H),6.54-6.52 (m, 4H), 6.37 (s, 1H), 2.85-2.80 (m, 4H), 1.95 (m, 2H), 1.77 (s, 3H), 0.98 (s, 6H) ppm

<Preparation of supported catalyst>

Manufacturing Example 1

Silica gel (SYLOPOL 952X, calcinated under 250°C, 100 g) was placed in a 2 L reactor under Ar, and MAO (766 mL) was slowly injected at room temperature, followed by stirring at 90°C for 15 hours. After completion of the reaction, cool to room temperature and leave for 15 minutes to decant the solvent with a cannula. Toluene (400 mL) was added, stirred for 1 minute, left for 15 minutes, and the solvent was decanted using a cannula.

700 μmol of the metallocene compound of Synthesis Example 1 was dissolved in 400 mL of toluene, and then transferred to a reactor using a cannula. After stirring at 50° C. for 5 hours, it was cooled to room temperature and allowed to stand for 15 minutes to decant the solvent using a cannula. 400 mL of toluene was added, stirred for 1 minute, left for 15 minutes, and decanted the solvent using a cannula twice. In the same way, 400 mL of hexane was added, stirred for 1 minute, and allowed to stand for 15 minutes to decant the solvent using a cannula, and an antistatic agent (Atmer 163, 3 g) was dissolved in 400 mL of hexane, and then transferred to the reactor using a cannula. After stirring at room temperature for 20 minutes, the solvent was removed by transferring to a glass filter.

Primary drying at room temperature under vacuum for 5 hours, and secondary drying under vacuum at 45° C. for 4 hours to obtain a supported catalyst.

Preparation Examples 2 to 12

Instead of the metallocene compound of Synthesis Example 1, a silica-supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compounds of Synthesis Examples 2 to 12 were used, respectively.

Comparative Preparation Examples 1 to 6

Instead of the metallocene compound of Synthesis Example 1, a silica-supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compounds of Comparative Synthesis Examples 1 to 6 were used, respectively.

<Preparation of propylene-ethylene random copolymer>

Example 1

In the presence of the silica-supported metallocene catalyst prepared in Preparation Example 1, bulk-slurry polymerization of propylene and ethylene was carried out using two continuous loop reactors.

At this time, the supported catalyst prepared according to Preparation Example 1 for bulk-slurry polymerization was used in the form of a mud catalyst mixed with oil and grease at 16 wt%. The thus-prepared catalyst mixture was introduced into a pre-polymerization reactor together with about 20 kg/hr of propylene, and after a residence time of at least 8 minutes had elapsed, it was continuously introduced into a loop reactor. At this time, hydrogen was introduced together with propylene flowing into the loop reactor, the reactor temperature was maintained at about 70°C, and the reactor pressure was maintained at about 35 kg/cm ² . At this time, the amount of hydrogen was added at about 150 ppm based on the propylene content introduced in a continuous manner. In addition, ethylene (C2) was directly introduced into the loop reactor so that the content of propylene (C3) in a continuous manner was 3.5 wt%, and a bulk-slurry polymerization process was performed.

Examples 2 to 12

In place of the silica-supported metallocene catalyst of Preparation Example 1, the bulk-slurry polymerization of propylene and ethylene was carried out in the same manner as in Example 1, except that the silica-supported metallocene catalysts of Preparation Examples 2 to 12 were used, respectively. I did.

Comparative Example 1

Bulk-slurry polymerization of propylene and ethylene was performed in the same manner as in Example 1, except that the input amount of ethylene (C2) was changed to be 2.0 wt% based on the content of propylene (C3).

Comparative Example 2

Bulk-slurry polymerization of propylene and ethylene was performed in the same manner as in Example 1, except that the input amount of ethylene (C2) was changed to be 2.6 wt% based on the content of propylene (C3).

Comparative Example 3

Instead of a metallocene catalyst, a Ziegler-Natta (Z/N) catalyst (manufacturer: Lyondellbasell, product name: ZN127VS) was used, and the amount of ethylene (C2) input was varied to be 3.0 wt% based on the propylene (C3) content. Except, bulk-slurry polymerization of propylene and ethylene was performed in the same manner as in Example 1.

Comparative Example 4

The same as in Example 1, except that the silica-supported catalyst prepared in Comparative Preparation Example 1 was used as the metallocene catalyst, and the input amount of ethylene (C2) was changed to be 2.0 wt% based on the propylene (C3) content. As a method, bulk-slurry polymerization of propylene and ethylene was carried out.

Comparative Example 5

Bulk-slurry polymerization of propylene and ethylene was carried out in the same manner as in Comparative Example 4, except that the input amount of ethylene (C2) was changed to be 2.5 wt% based on the propylene (C3) content.

Comparative Example 6

Propylene and ethylene were mixed in the same manner as in Comparative Example 4, except that the input amount of ethylene (C2) was changed to be 3.5 wt% based on the propylene (C3) content.

Bulk-slurry polymerization was performed, but fouling occurred in the polymerization process.

Comparative Example 7

The same as in Example 1, except that the silica-supported catalyst prepared in Comparative Preparation Example 2 was used as the metallocene catalyst, and the input amount of ethylene (C2) was changed to be 3.0 wt% based on the propylene (C3) content. As a method, bulk-slurry polymerization of propylene and ethylene was performed.

Comparative Example 8

Bulk-slurry polymerization of propylene and ethylene was carried out in the same manner as in Comparative Example 7, except that the input amount of ethylene (C2) was changed to be 4.5 wt% based on the content of propylene (C3).

Comparative Example 9

Bulk-slurry polymerization of propylene and ethylene was performed in the same manner as in Comparative Example 7, except that the input amount of ethylene (C2) was changed to be 6.0 wt% based on the content of propylene (C3), but fouling in the polymerization process (Fouling) occurred.

Comparative Example 10

The same as in Example 1, except that the silica-supported catalyst prepared in Comparative Preparation Example 3 was used as the metallocene catalyst, and the amount of ethylene (C2) input was changed to be 6.0 wt% based on the propylene (C3) content. As a method, bulk-slurry polymerization of propylene and ethylene was performed.

Comparative Example 11

The same as in Example 1, except that the silica-supported catalyst prepared in Comparative Preparation Example 4 was used as the metallocene catalyst, and the input amount of ethylene (C2) was changed to be 5.5 wt% based on the propylene (C3) content. As a method, bulk-slurry polymerization of propylene and ethylene was performed.

Comparative Example 12

The same as in Example 1, except that the silica-supported catalyst prepared in Comparative Preparation Example 5 was used as the metallocene catalyst, and the input amount of ethylene (C2) was changed to be 4.5 wt% based on the propylene (C3) content. As a method, bulk-slurry polymerization of propylene and ethylene was performed.

Comparative Example 13

The same as in Example 1, except that the silica-supported catalyst prepared in Comparative Preparation Example 6 was used as the metallocene catalyst, and the input amount of ethylene (C2) was changed to be 2.0 wt% based on the propylene (C3) content. As a method, bulk-slurry polymerization of propylene and ethylene was performed.

<Experimental Example>

Evaluation of properties of propylene-ethylene random copolymer

The propylene-ethylene random copolymers prepared in the above Examples and Comparative Examples were evaluated for physical properties by the following method.

(1) Content of comonomer (C2, wt%)

According to the American Society for Testing and Materials specification ASTM D 5576, a propylene - After fixing the film or the film type specimens of the ethylene random copolymer to Magnetic holder of the FT-IR equipment, 4800 ~ 3500 cm reflecting the sample thickness in the IR absorption ^{spectrum 1} Measure the area of the 710~760 cm ^-1 peak where the ethylene component of the peak appears, and divide the measured value by dividing the area of the 710~760 cm ^-1 peak of the standard sample by the height of 4800~3500 cm ^-1 peak. The comonomer content was calculated by substituting into the calibration equation obtained by plotting.

(2) Melting point (Tm) and crystallization temperature (Tc)

The melting point, melting point (Tm) and crystallization temperature (Tc) of the propylene polymer were measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer is heated to 200° C., maintained at that temperature for 5 minutes, then lowered to 30° C., and the temperature is increased again, so that the top of the DSC (Differential Scanning Calorimeter, manufactured by TA) curve is the melting point (Tm). When the temperature was lowered to 30 °C again, the top of the curve was measured as the crystallization temperature (Tc). At this time, the rate of rise and fall of the temperature was 10 °C/min, and the melting point (Tm) and crystallization temperature (Tc) were measured in a section where the second temperature rises and falls.

(3) melt index (MI)

According to the American Society for Testing and Materials Standard ASTM D 1238, it was measured with a load of 2.16 kg at 230° C., and expressed as the weight (g) of the polymer melted for 10 minutes.

(4) Haze (%)

According to the American Society for Testing and Materials standard ASTM D1003, the degree of refraction of light (%) when light was irradiated on 1T (1mm) of a propylene-ethylene random copolymer specimen was measured. Haze was measured as Td (refracted light) / Tt (passed light) × 100 (%) of the transparency of the specimen.

(5) Xylene Soluble (X.S: Xylene Soluble, wt%)

Xylene was added to each sample of the propylene-ethylene random copolymer, heated at 135° C. for 1 hour, and cooled for 30 minutes to perform pretreatment. Xylene flows for 4 hours at a flow rate of 1 mL/min in OminiSec (Viscotek, FIPA) equipment, and RI (Refractive Index), DP (Pressure across middle of bridge), IP (Inlet pressure through bridge top) When the base line of (to bottom) stabilized, the concentration of the pretreated sample and the amount of injection were recorded and measured, and then the peak area was calculated.

(6) Total volatile organic compound emission (TVOC, ppm)

According to the VDA 277 method, a total volatile organic compound emission amount (TVOC, Toatal Volatile Organic Compound, ppm) included in the propylene-ethylene random copolymer was measured using a Headspace-GC (Gas chromatography) apparatus.

The evaluation results of the properties of the propylene-ethylene random copolymer measured by the method described above are shown in Table 1 below.

Polymerization process Properties of the copolymer catalyst C2
input
(wt%) C2 content
(IR analysis wt%) Tm
(℃) Random Tc
(℃) MI
(g/10min) Haze
(%) XS
(wt%) TVOC (ppm) Example 1 Manufacturing Example 1 3.5 4.3 125.2 73.0 18.8 7.1 0.6 58 Example 2 Manufacturing Example 2 3.5 4.2 126.2 73.8 19.1 7.2 0.7 55 Example 3 Manufacturing Example 3 3.5 4.3 125.4 72.5 19.1 7.1 0.8 55 Example 4 Manufacturing Example 4 3.5 4.2 125.4 72.6 19.2 7.3 0.6 58 Example 5 Manufacturing Example 5 3.5 4.2 125.5 72.8 19.5 7.2 0.7 55 Example 6 Manufacturing Example 6 3.5 4.2 125.3 72.8 18.5 7.2 0.8 58 Example 7 Manufacturing Example 7 3.5 4.1 125.3 73.5 18.4 7.4 0.6 58 Example 8 Manufacturing Example 8 3.5 4.2 125.4 73.1 18.4 7.3 0.8 57 Example 9 Manufacturing Example 9 3.5 4.2 125.2 73.2 18.6 7.3 0.7 56 Example 10 Manufacturing Example 10 3.5 4.2 125.1 73.0 18.6 7.2 0.7 57 Example 11 Manufacturing Example 11 3.5 4.3 125.8 72.8 18.4 7.1 0.7 55 Example 12 Manufacturing Example 12 3.5 4.2 125.6 73.8 18.5 7.2 0.8 58 Comparative Example 1 Manufacturing Example 1 2.0 2.6 134.6 85.5 18.1 8.3 0.8 54 Comparative Example 2 Manufacturing Example 1 2.6 3.3 130.6 80.1 18.5 7.8 0.6 56 Comparative Example 3 Z/N 3.0 5.2 138.1 111 18 8.3 4.5 310 Comparative Example 4 compare
Manufacturing Example 1 2.0 2.3 131.1 83.1 18.4 8.5 0.6 56 Comparative Example 5 compare
Manufacturing Example 1 2.5 2.8 125.8 73.5 19.3 8.1 0.6 61 Comparative Example 6 compare
Manufacturing Example 1 3.5 Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible Comparative Example 7 compare
Manufacturing Example 2 3.0 2 132.1 83.8 19.1 8.8 0.8 58 Comparative Example 8 compare
Manufacturing Example 2 4.5 2.8 126.1 74.5 20 8.2 0.6 56 Comparative Example 9 compare
Manufacturing Example 2 6.0 Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible Comparative Example 10 compare
Manufacturing Example 3 6.0 3.5 126.1 78.1 18.2 7.8 0.6 56 Comparative Example 11 compare
Manufacturing Example 4 5.5 3.3 125.8 77.1 19.6 7.7 0.7 50 Comparative Example 12 compare
Manufacturing Example 5 4.5 2.6 125.7 76.8 20.1 8.3 1.1 54 Comparative Example 13 compare
Manufacturing Example 6 2.0 Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible Measure
Impossible

As shown in Table 1, the propylene-ethylene random copolymers of Examples 1 to 12 according to the present invention secure a high melting point (Tm) of 125.2 °C to 126.2 °C to maintain process stability and other injection properties, and ethylene ( In addition to being able to increase the C2) content, it was confirmed that the increased ethylene (C2) content exhibited a characteristic of lowering the crystallinity, thereby improving transparency. In addition, in the case of Examples 1 to 12, it can be seen that the TVOC is remarkably low, and eco-friendliness can be secured with a highly transparent propylene-ethylene random copolymer used for food containers and the like.

On the other hand, even in the case of Comparative Examples 1 and 2 using the same catalyst precursor of Preparation Example 1 as in Example 1, the content of ethylene (C2) decreased as the amount of ethylene (C2) input in the polymerization process decreased, resulting in a haze of 8.3. It appears as high as% and 7.8%, and it can be seen that transparency is poor.

In addition, Comparative Example 3 using a Ziegler-Natta (Z/N) catalyst, despite the high ethylene (C2) content, was a blocky non-uniform copolymerization of ethylene (C2) in the polymer structure, resulting in the crystallization temperature (Tc ) Was very high at 111 ℃, TVOC was extremely high at 310 ppm, and the atactic xylene soluble content was also very high at 4.5 wt%.

On the other hand, in the case of Comparative Examples 4 to 6 using a catalyst composition containing a metallocene compound of a ligand containing a generally known cyclopentadienyl without an indacene ligand, when maintaining the Tm range in which fouling does not occur There was a limit to increasing the ethylene (C2) content, so it was not possible to reach a certain degree of transparency. In particular, in the case of Comparative Example 6, fouling occurred in the polymerization process, and physical property evaluation of the copolymer could not be performed.

Similarly, in the case of Comparative Examples 7 to 9 using the catalyst composition of Comparative Preparation Example 2 including a metallocene compound having an indene ligand bridged instead of a cyclopentadienyl (Cp) ligand bridged with an indacene ligand, basically Since the Tm of homopolypropylene itself is low, if the ethylene (C2) content is raised, fouling occurs, and a certain level of ethylene (C2) content cannot be maintained. Moreover, since ethylene (C2) reactivity was not good, the amount of ethylene (C2) input had to be very high in order to secure an equivalent level of ethylene content in the copolymer. In particular, in the case of Comparative Example 9, fouling occurred in the polymerization process, and physical property evaluation of the copolymer could not be performed.

In addition, in the case of Comparative Examples 10 to 12 using a catalyst composition containing a metallocene compound having a bis-indenyl (or indacenyl) group, the ethylene conversion rate (C2 conversion) is very low, and the amount of ethylene (C2) inputted is high. The ethylene (C2) content in the body could be raised to a certain level or more, and this also had a limit in increasing the ethylene (C2) content, and thus a certain transparency could not be reached.

On the other hand, in the case of Comparative Example 13, atactic polypropylene was produced due to a structure that could not have racemo selectivity that gives the directionality of polypropylene, and the evaluation of physical properties of the copolymer was not possible.

Claims (11)

The melting point (Tm) is 125°C or higher,
The content of ethylene is at least 4.0% by weight,
The crystallization temperature (Tc) is 75 °C or less,
The melt index (MI _2.16 , melt index measured at 230 °C, 2.16 kg load) is 16 g/min to 22 g/min,
Propylene-ethylene random copolymer.
The method of claim 1,
The melting point (Tm) is 125 ℃ to 150 ℃,
Propylene-ethylene random copolymer.
The method of claim 1,
The content of ethylene is 4.0% to 5.5% by weight,
Propylene-ethylene random copolymer.
The method of claim 1,
The crystallization temperature (Tc) is 65 ℃ to 75 ℃,
Propylene-ethylene random copolymer.
The method of claim 1,
Xylene soluble content (XS, Xylene soluble) is 1.0% by weight or less,
Propylene-ethylene random copolymer.
The method of claim 1,
Haze measured according to the ASTM 1003 method is 7.5% or less,
Propylene-ethylene random copolymer.
The method of claim 1,
The total volatile organic compound emission (TVOC) measured according to the VDA 277 method is 70 ppm or less,
Propylene-ethylene random copolymer.
The method of claim 1,
Prepared by copolymerizing a propylene monomer and an ethylene comonomer in the presence of a catalyst composition comprising a metallocene compound of Formula 1 below,
Propylene-ethylene random copolymer:
[Formula 1]

In Formula 1,
M is a Group 4 transition metal,
X ¹ and X ² are the same as or different from each other, and each independently a halogen element,
R ¹ and R ² are the same as or different from each other, and each independently C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkoxyalkyl, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 arylalkyl,
R ³ to R ⁶ are the same as or different from each other, and each independently C _1-20 alkyl,
R ⁷ is substituted or unsubstituted C _6-20 aryl,
R ⁸ is C _1-20 alkyl.
The method of claim 8,
R ¹ and R ² are each C _1-8 straight or branched chain alkyl, or C _2-12 straight or branched chain alkoxyalkyl;
R ³ to R ⁶ are each C _1-6 straight or branched chain alkyl;
M is zirconium or hafnium;
R ⁷ is phenyl, phenyl substituted with C _1-6 straight or branched chain alkyl, naphthyl, or naphthyl substituted with C _1-6 straight or branched chain alkyl;
R ⁸ is C _1-6 straight or branched chain alkyl,
Propylene-ethylene random copolymer.
The method of claim 8,
The metallocene compound is represented by the following formula 1-1,
Propylene-ethylene random copolymer:
[Formula 1-1]

In Formula 1-1,
M, X ¹ , X ² , R ¹ , R ² , R ⁷ are as defined in claim 8.
The method of claim 8,
The metallocene compound is any one of the compounds represented by the following structural formula,
Propylene-ethylene random copolymer:

.