KR102502159B1 - Propylene-ethylene random copolymer - Google Patents

Abstract

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

Description

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

The present invention relates to propylene-ethylene random copolymers.

Polypropylene is a general-purpose resin that is easy to process and has excellent physical properties compared to its price, replacing traditional materials such as glass, wood, paper, and metal, or expanding its application range to other plastics and even engineering plastics. am.

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

On the other hand, catalysts for polypropylene polymerization can be largely classified into Ziegler-Natta catalysts and metallocene catalysts. In the case of the Ziegler-Natta catalyst, since it is a multi-site catalyst in which several active sites are mixed, It is characterized by a wide molecular weight distribution, and there is a problem that there is a limit to securing desired physical properties because the composition distribution of comonomers is not uniform. In particular, when random copolymerization with ethylene is performed to secure transparency in the presence of a Ziegler-Natta catalyst (Z/N, ziegler-natta), the polymerizability of ethylene is very high, resulting in a non-uniform copolymerization, i.e., a heterogeneous polymer. , there is a problem in that ethylene polymers between propylene polymers, which are not repeating structures, are formed as blocks, resulting in significant deterioration in physical properties and high volatile organic compound emissions (VOC).

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst composed of an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst. It is possible to prepare a polymer with a narrow molecular weight distribution and a uniform comonomer composition distribution according to the characteristics of a single active point. In addition, the tacticity, copolymerization characteristics, molecular weight, and crystallinity of the polymer may be changed according to the modification of the ligand structure of the catalyst and the change of the polymerization conditions.

In particular, as the recent environment-related awareness change seeks to reduce the generation of volatile organic compounds (VOCs) in many product groups, in the case of various commercially available polypropylenes, products with Ziegler-Natta catalysts are the mainstream, but food containers Recently, the conversion to polypropylene resin products using metallocene catalysts that have low odor and low elution characteristics as an eco-friendly material such as lamp is accelerating.

However, when producing polypropylene using a known metallocene catalyst, there is a limit to increasing the content of ethylene, a comonomer, due to its low melting point compared to that of Ziegler-Natta catalysts, and thus crystallization in injection products is limited. There is a difficulty in implementing high transparency while lowering it.

Therefore, it is required to develop a method for producing high transparency polypropylene useful for injection products by using a metallocene catalyst, not only having a low total volatile organic compound emission (TVOC) but also maximizing an ethylene content.

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

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

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 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) of 70 ppm or less, measured according to the VDA 277 method. .

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 represented by 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 are each independently a halogen element;

R ¹ and R ² are the same as or different from each other, and are 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 represents C _1-20 alkyl;

R ⁷ is a substituted or unsubstituted C _6-20 aryl;

R ⁸ is C _1-20 alkyl.

In this case, in Formula 1, R ¹ and R ² may each be C _1-8 straight-chain or branched-chain alkyl, or C _2-12 straight-chain or branched-chain 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-chain or branched-chain alkyl or C _1-3 straight-chain or branched-chain alkyl, specifically methyl, ethyl, propyl, or isopropyl, iso It can be propyl, preferably methyl.

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

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

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

In addition, the metallocene compound represented by Chemical Formula 1 may be, for example, represented by Chemical Formula 1-1 below.

[Formula 1-1]

In Formula 1-1, M, X ¹ , X ² , R ¹ , R ² , and 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.

.

.

Terms used in this 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 dictates otherwise.

In this specification, terms such as "comprise", "comprise" or "having" are used to describe an implemented feature, number, step, component, or combination thereof, and one or more other features, numbers, or steps. , components, combinations or additions thereof are not excluded.

Also, in this specification, when each layer or element is referred to as being formed “on” or “above” each layer or element, it means that each layer or element is formed directly on each layer or element, or other This means that layers or elements may be additionally formed between each layer or on the object or substrate.

Since the present invention can have various changes and various forms, specific embodiments will be exemplified and described in detail below. However, it should be understood that this does not limit the present invention to the specific disclosed form, and includes all modifications, equivalents, and substitutes included in the spirit and technical scope of the present invention.

Hereinafter, the present invention will be described in detail.

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

Propylene (co)polymers prepared with a Ziegler-Natta catalyst have a problem in that rigidity is greatly reduced due to a decrease in crystal properties and volatile organic compound emissions (VOC) are high. In addition, even when using a conventional metallocene catalyst, fouling occurs in the polymerization process due to its low melting point, and there is a limit to increasing the content of ethylene, a comonomer. It is necessary to improve processability so that it is suitable for molding.

Accordingly, according to the present invention, a high transparency propylene-ethylene random copolymer for injection molding having a low total volatile organic compound emission (TVOC), high rigidity and excellent processability can be provided.

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

The propylene-ethylene random copolymer according to one 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 a homo-polypropylene resin and realize high copolymerizability with ethylene by using a metallocene catalyst having a novel structure as described below, thereby achieving 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 one 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, fouling does not occur in the polymerization process, and excellent processability and heat resistance can be exhibited. 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 is possible to have a low haze value and secure high transparency. 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 there is.

In the present invention, the melting point (Tm) and 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 raising the temperature, maintaining it at that temperature for 5 minutes, then lowering it to 30 ° C., and then increasing the temperature again to obtain a DSC (Differential Scanning Calorimeter, manufactured by TA) curve The temperature corresponding to the top is taken as the melting point (Tm). After that, when the temperature is lowered to 30 ℃ again, the top of the curve is taken as the crystallization temperature (Tc). At this time, the rate of temperature rise and fall is 10 °C/min, and the melting point (Tm) and crystallization temperature (Tc) are shown as the results measured in the second temperature rising and falling section.

In addition, as described above, 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 the ethylene content is increased while maintaining a high melting point, it is possible to have a low haze value and secure high transparency when applied to an injection product such as a film. More specifically, the propylene-ethylene random copolymer may have an ethylene content of 4.1 wt% or more, or 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, heterogeneous comonomers enter between the main chains to deform the lamellar structure of the resin, thereby lowering the melting point (Tm) and balancing stiffness and impact strength. ) was not maintained or it was difficult to secure process stability. In contrast, in the present invention, a metallocene catalyst having a novel structure as described below can be used to secure a very high melting point in a homo-polypropylene resin and realize high copolymerizability with ethylene, so that even with such a high ethylene content, a high melting point of 125 ° C. or more can be obtained. It can exhibit improved physical properties that maintain the melting point.

In the present invention, the content of ethylene, a comonomer, in the propylene-ethylene random copolymer is determined according to ASTM D 5576 of the American Society for Testing and Materials. After fixing to , the height of the 4800 cm ^-1 to 3500 cm ^-1 peak reflecting the thickness of the specimen in the IR absorption spectrum and the area of 710 cm ^-1 to 760 cm ^-1 where the ethylene component appears are measured, respectively, and the measured values 710 cm ^-1 to 760 cm ^-1 peak area of the standard sample divided by the peak height of 4800 cm ^-1 to 3500 cm ^-1 is substituted into the calibration equation obtained by plotting the comonomer content can be calculated

Meanwhile, the propylene-ethylene random copolymer according to one embodiment of the present invention has a melt index (MI _2.16 ) of about 16 g/10 min to about 16 g/10 min as measured under 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/10 min. By optimizing the range of the melt index in this way, it is possible to obtain a highly transparent product while maintaining excellent processability during thread 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/10 min, the processability is poor and the injection pressure is increased so that injection cannot be performed, and when it exceeds about 22 g/10 min, the viscosity Since it flows down and cannot be injected, it cannot be used as a resin for injection.

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 conventional polypropylene applied with a Ziegler-Natta catalyst or polypropylene applied with a conventional metallocene catalyst. And, by optimizing the low crystallinity temperature (Tc) and melt index (MI _2.16 , 230 ℃, melt index measured under 2.16 kg load) of 75 ℃ or less to 16 to 22 g / min, excellent in polymerization process and injection molding While securing processability, the total volatile organic compound emission (TVOC) is low, and high transparency can be exhibited with high rigidity.

For example, in the propylene-ethylene random copolymer according to one embodiment of the present invention, the xylene soluble content (X.S, Xylene soluble) may be about 1.0% by weight or less, or about 0.85% by weight or less, or about 0.7% by weight or less there is. As such, the low xylene soluble content is a value representing the content of the atactic component in the entire copolymer, and the lower the content thereof, the lower the degree of stickiness 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 a low xylene soluble content, so that the possibility of process defects occurring during processing and heat sealing is extremely low.

In addition, the propylene-ethylene random copolymer may exhibit high transparency with a haze of about 7.5% or less, about 7.3% or less, or about 7.2% or less, measured according to the 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 (TVOC) of about 70 ppm or less, or about 65 ppm or less, or about 60 ppm or less, measured according to the VDA 277 method. By having such a low total volatile organic compound emission amount (TVOC), eco-friendliness can be secured as a propylene-ethylene random copolymer for transparent injection used in food containers and the like.

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

A propylene random copolymer according to an embodiment of the present invention having physical and structural characteristics as described above is a propylene monomer and an ethylene comonomer in the presence of a catalyst composition comprising a metallocene compound represented by Formula 1 as a catalytically active component It can be prepared by a manufacturing method comprising the step of random copolymerization.

[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 are each independently a halogen element;

R ¹ and R ² are the same as or different from each other, and are 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 represents C _1-20 alkyl;

R ⁷ is a substituted or unsubstituted C _6-20 aryl;

R ⁸ is C _1-20 alkyl.

On the other hand, in the present specification, the following terms may be defined as follows unless there is a particular 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 straight-chain, branched-chain or cyclic alkyl. Specifically, alkyl having 1 to 20 carbon atoms is straight-chain alkyl having 1 to 20 carbon atoms; straight-chain alkyl of 1 to 15 carbon atoms; straight-chain alkyl of 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 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 (C _2-20 ) carbon atoms includes straight-chain or branched-chain alkenyl, and specifically includes allyl, allyl, ethenyl, propenyl, butenyl, pentenyl, and the like. but not limited to

Examples of the alkoxy group having 1 to 20 carbon atoms (C _1-20 ) include methoxy group, ethoxy group, isopropoxy group, n-butoxy group, tert-butoxy group group, phenyloxy group group, and cyclohexyloxy group group. it is not going to be

An alkoxyalkyl group having 2 to 20 carbon atoms (C _2-20 ) is a functional group in which one or more hydrogens of the aforementioned alkyl are substituted with alkoxy, specifically methoxymethyl, methoxyethyl, ethoxymethyl, iso-propoxymethyl, alkoxyalkyl such as iso-propoxyethyl, iso-propoxypropyl, iso-propoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxypropyl, 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 (C _1-20 ) carbon atoms is 1 to 3 hydrogens of -SiH ₃ are converted to 1 to 3 alkyl or alkoxy as described above. A substituted functional group, specifically, alkylsilyl such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl or dimethylpropylsilyl; alkoxysilyl such as methoxysilyl, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl; Alkoxyalkylsilyl such as methoxydimethylsilyl, diethoxymethylsilyl or dimethoxypropylsilyl may be mentioned, but 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 the alkyl as described above are substituted with silyl, specifically -CH ₂ -SiH ₃ , methylsilylmethyl or dimethylethoxysilylpropyl, etc. It may include, but is not limited thereto.

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

An aryl of 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, and the like, but is not limited thereto.

Alkylaryl having 7 to 20 carbon atoms (C _7-20 ) may mean a substituent in which one or more hydrogens of an aromatic ring are substituted with the above-mentioned alkyl. As an example, the alkylaryl having 7 to 20 carbon atoms (C _7-20 ) includes 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 one or more hydrogens of the above-mentioned alkyl are substituted by the above-mentioned aryl. As an example, the arylalkyl having 7 to 20 carbon atoms (C _7-20 ) may include phenylmethyl, phenylethyl, biphenylmethyl, naphthylmethyl, etc., but is not limited thereto.

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

And, the Group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf), or rutherfordium (Rf), specifically titanium (Ti), zirconium (Zr), or hafnium (Hf) It may be, 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 may be boron (B) or aluminum (Al). and is not limited thereto.

The above-mentioned substituents are optionally hydroxy groups within the range of exhibiting the same or similar effects to the desired effect; halogen; alkyl or alkenyl, aryl, alkoxy; Alkyl or alkenyl, aryl, alkoxy containing at least one heteroatom 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 sulfone groups.

The catalyst composition used for preparing the propylene-ethylene random copolymer according to an embodiment of the present invention includes the compound of Chemical Formula 1 as a single metallocene catalyst. Accordingly, it can be confirmed that the molecular weight distribution can be significantly narrowed compared to the conventional propylene copolymer prepared by mixing two or more catalysts, and thus the stiffness 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 linked up and down by bridges as ligands.

Specifically, in Formula 1, an alkyl group-substituted cyclopentadienyl group is connected to the bridge at the upper side of the ligand, and 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 it can have various characteristics or selective advantages of two different cyclopentadienyls, it can exhibit better catalytic activity.

Specifically, the cyclopentadienyl structure has a hydrogen functional group substituted with an alkyl group to maintain a constant three-dimensional spatial arrangement (steric) when forming polypropylene, thereby securing isotacticity and maintaining high activity. there is. In the case of cyclopentadienyl (Cp) substituted only with hydrogen, since there is no bulky part, when propylene is inserted, the catalyst faces in a completely open state, so the tacticity collapses, resulting in atactic polypropylene (atactic polypropylene). PP) is formed.

In addition, when propylene (C3) and H ₂ are reacted together, the reaction occurs competitively. When 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 arrangement is given to the metal center, so that the reactivity of H ₂ , which is smaller than that of 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 is bonded to position 2 of the indacenyl structure, hydrogen reactivity can be increased in the polymerization process.

In addition, by including an aryl substituent capable of donating electrons at position 4 of the indacenyl structure in abundance, for example, a C _6-20 aryl substituent in which R ⁷ is substituted or not, the bridge of Formula 1 Since electrons are abundantly donated to metal atoms included in the structure, higher catalytic activity can be secured.

In particular, in the case of the indacenyl structure of the metallocene compound represented by Chemical Formula 1, a very excellent effect can be obtained in an active part in combination with cyclopentadienyl rather than a general indenyl structure. This is because in the steric effect of cyclopentadienyl, it is possible to secure a flat structure in which the indacenyl structure faces the indenyl structure, thereby having a certain effect on the active site, thereby contributing to the activation of the propylene monomer. It seems to work very favorably. These results can be confirmed by an increase in tacticity of the polymerized polypropylene.

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

At this time, 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-chain or branched-chain alkyl or C _2-12 straight-chain or branched-chain 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-chain or branched-chain alkyl or C _1-3 straight-chain or branched-chain alkyl, specifically methyl, ethyl, propyl, or isopropyl, iso It can be propyl, preferably methyl.

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

Substituents at each position of the aromatic group can supply enough electrons to the aromatic group by an inductive effect, increase the overall size of the metallocene compound, and increase the available angle, thereby facilitating access of monomers. As a result, better catalytic activity can be exhibited.

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

In addition, the metallocene compound represented by Chemical Formula 1 may be, for example, represented by Chemical Formula 1-1 below.

[Formula 1-1]

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

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

.

.

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

Meanwhile, in the method for preparing the metallocene compound or catalyst composition of the present invention, equivalent weight (eq) means molar equivalent weight (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 Chemical Formula 1 on a carrier together with a cocatalyst compound.

In the supported metallocene catalyst according to the present invention, the cocatalyst supported on the carrier to activate the metallocene compound is an organometallic compound containing a Group 13 metal, and polymerizes olefins under a general metallocene catalyst It is not particularly limited as long as it can be used when doing.

Specifically, the cocatalyst compound may include one or more aluminum-containing cocatalysts represented by Formula 2 below.

[Formula 2]

-[Al(R ²² )-O] _m -

In Formula 2, R ²² are the same as or different from each other, and each independently represents halogen, C _1-20 alkyl or C _1-20 haloalkyl; m is an integer greater than or equal to 2;

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

For example, the cocatalyst of Chemical Formula 2 may be an alkylaluminoxane-based compound in which repeating units are bonded in a linear, circular or network shape, and specific examples of such a cocatalyst include methylaluminoxane (MAO) and ethylaluminoxane. , isobutyl aluminoxane or butyl aluminoxane, and the like.

In the supported metallocene catalyst according to the present invention, the mass ratio of all transition metals included in the metallocene compound represented by Chemical Formula 1 to the support may be 1:10 to 1:1000. When the carrier and the metallocene compound are included in the above mass ratio, an optimal shape can 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, preferably having a highly reactive hydroxy group and a siloxane group that is dried to remove moisture from the surface A carrier may be used.

For example, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are typically 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., the moisture on the surface is too high, and the moisture on the surface and the cocatalyst react. This is undesirable because only siloxane remains and the reaction site with the cocatalyst decreases.

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

If the amount of the hydroxy group is less than 0.1 mmol / g, there are few reaction sites with the cocatalyst, and if it exceeds 10 mmol / g, it is not preferable because it may originate from moisture in addition to the hydroxy group present on the surface of the carrier particle. not.

Meanwhile, the propylene-ethylene random copolymer according to the present invention can be produced by copolymerizing monomers and comonomers in the presence of the above-described metallocene catalyst.

The polymerization reaction may be carried out by contacting and copolymerizing propylene monomers and comonomers using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

And, the polymerization temperature may be about 25 ℃ to about 500 ℃, preferably about 25 ℃ to about 200 ℃, more preferably about 50 ℃ to about 100 ℃. 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 , and 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, specifically 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 of hydrogen gas 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 within the above-mentioned content range A 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 aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane, and chlorobenzene. It can be injected by dissolving or diluting in a hydrocarbon solvent substituted with a chlorine atom. The solvent used here is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkyl aluminum, and it is also possible to use a cocatalyst further.

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 increased ethylene content, has a low crystallization temperature and an appropriate melting index, and thus has excellent process stability, processability, and extrusion characteristics, along with high stiffness. 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 can be preferably applied to products for high-transparency thin film injection molding as an eco-friendly material.

Propylene-ethylene random copolymer according to the present invention. It maintains a high melting point, secures excellent physical properties such as rigidity and impact strength, and process stability without fouling. It can express the characteristics of lowering the crystallinity by increasing the crystallinity, and the total volatile organic compound emission (TVOC) is remarkably low, which is advantageous for manufacturing highly transparent injection-molded products used as eco-friendly materials such as food containers.

Hereinafter, the action and effect of the invention will be described in more detail through specific examples 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. In another reactor, 2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) was added 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. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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/diethylether, Toluene/Ether, volume ratio 2/1, 0.53 M), n-BuLi (2.05 eq) was added at -25 ° C, and then 5 Stir for an hour. In a separate flask, a slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) was prepared, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried to obtain the title metallocene compound.

For the transition metal compound thus obtained, NMR data was measured using 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. In another reactor, 2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) was added 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. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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) with toluene (0.17 M) was prepared in a separate flask, added to the ligand solution, and stirred overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (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 (1 eq) was mixed with toluene / tetrahydrofuran (Toluene / THF ) was dissolved in a mixed 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. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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. In a separate flask, a slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) was prepared, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (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 After dissolving in ), n-BuLi (1.05 eq) was slowly added dropwise at -25 ° C, followed by stirring at room temperature for 3 hours. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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. In a separate flask, a slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) was prepared, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. Mixing 2-Methyl-4-(2'-naphthylene) Indacene (1 eq) with toluene/tetrahydrofuran (Toluene/THF) 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. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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. In a separate flask, a slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) was prepared, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred 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. In another reactor, 2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) was added 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. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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. In a separate flask, a slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) was prepared, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred 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. In another reactor, 2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) was added 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. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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. In a separate flask, a slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) was prepared, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred 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. In another reactor, 2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) was added 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. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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. In a separate flask, a slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) was prepared, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred 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. In another reactor, 2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) was added 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. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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. In a separate flask, a slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) was prepared, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred 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. In another reactor, 2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) was added 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. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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. In a separate flask, a slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) was prepared, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (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 (1 eq) was added to toluene/tetrahydrofuran ( After dissolving in a mixed solvent (volume ratio of 3/2, 0.5 M) of Toluene/THF), n-BuLi (1.05 eq) was slowly added dropwise at -25 ° C, followed by stirring at room temperature for 3 hours. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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) with toluene (0.17 M) was prepared in a separate flask, added to the ligand solution, and stirred overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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

After dissolving 2,3,4,5-tetramethylcyclopentadiene (TMCP, 2,3,4,5-tetramethylcyclopentadien) in tetrahydrofuran (THF), n-butyllithium (n-BuLi, 1.05 After slowly adding eq) dropwise, the mixture was stirred at room temperature for 3 hours. Thereafter, dichloro 6-(tertbutoxyhexylmethyl silane, 1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. In another reactor, 2-Methyl-4-(3',5'-ditertbutylphenyl) Indacene (1 eq)) was added 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. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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) with toluene (0.17 M) was prepared in a separate flask, added to the ligand solution, and stirred overnight at room temperature. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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. Then, dichloro dimethyl Silane (1.05 eq) was added at -10 °C, followed by stirring at room temperature overnight. After dissolving 2-Methyl-4-(4'-tertbutylphenyl)indene (1 eq) in Toluene/THF (3/2, 0.5M) in another reactor, n-BuLi (1.05 eq) was slowly added dropwise at -25 °C. Then, the mixture was stirred at room temperature for 3 hours. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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) with toluene (1.2 M) was prepared in a separate flask, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried to obtain the title metallocene compound.

Comparative Synthesis Example 2

Preparation of 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, then dichloro dimethyl Silane (0.53 eq) was added at -10 °C and stirred overnight at room temperature. Thereafter, the mixture was stirred at room temperature overnight, worked up using 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. In a separate flask, a slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) was prepared, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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) -inden-1-yl) silane preparation

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

Transition metal compounds Dimethylsilanediyl(4-(4'-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacen-7-yl)(2-isopropyl-4-(4'-tertbutylphenyl) Preparation of )-inden-1-yl) 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 (1.2 M) was prepared in a separate flask, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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 well stirred AlCl ₃ (100 g, 750 mmol) in CH ₂ Cl ₂ (600 mL) at -70 °C. After 20 min, 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, aq. NaHCO ₃ , dried over MgSO ₄ and evaporated. Vacuum distilled (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 CH ₂ Cl ₂ (50 mL) prepared earlier was added to a suspension of AlCl ₃ (40 g, 300 mmol) in CH ₂ Cl ₂ (250 mL) at -20 °C. After stirring 20 min, 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) to obtain 31 g (74%) of the reaction product, namely 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 above 2-methyl- 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 stirred at reflux for 6 hours, cooled, poured into water (700 mL) and extracted with benzene (4 times 100 mL each). 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 obtained by 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 above 4-(4-tert-butylphenyl)-2-methyl2,3,5,6,7,8-hexahydro-1H- in Et ₂ O (150 mL). 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 50 mL each). 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 with a Dean Stark head (controlled by TLC, benzene/EtOAc 4:1) within 4 hours. The resulting solution was then washed with water, aqueous KHCO ₃ , dried over MgSO ₄ , passed through silica gel, and evaporated to yield 12.8 g (81%) of the reaction product, 9-(4-tert- Butylphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene was obtained.

The above 9-(4-tert-butylphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene (2.97 g, 9.38 mmol) 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 min, 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 hexanes (200 mL) were added, 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 hexanes, 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 min, 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 yellow-orange powder was dried, dimethoxyethane (100 mL) and LiCl (0.3 g) were added, and the mixture was refluxed with stirring for 6 hours. Subsequent recrystallization from dimethoxyethane and CH ₂ Cl ₂ /Et ₂ O gave the product. The yield of the lac-form was 0.88 g (24.4%).

Comparative Synthesis Example 5

Preparation of 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 for 3 hours at room temperature. After separating the transparent organic layer from the mixed solution, excess trichloromethylsilane was removed by vacuum drying the separated transparent organic layer to obtain a transparent liquid (6-t-butoxyhexyl)dichloromethylsilane.

15.4 mL of an n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise to 77 mL of a 2-methyl-4-phenylindene toluene/THF=10/1 solution (34.9 mmol) at 0 °C and then 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 previously was slowly added dropwise to the mixed solution at -78 °C, and stirred for about 10 minutes and then stirred at 80 °C for 1 hour. Then, water was added to separate the organic layer, followed by silica column purification and 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

In 50 mL of 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 After slowly adding 3.0 mL of lithium solution (2.5 M in hexane) dropwise at -78 °C, the mixture was stirred at room temperature for about 2 hours and vacuum dried. After washing the salt with hexane, it was filtered and vacuum dried to obtain a yellow solid. Ligand salt and bis(N,N'-diphenyl-1,3-propanediamido)dichlorozirconium bis(tetrahydrofuran) [Zr(C ₅ H ₆ After weighing NCH ₂ CH ₂ NC ₅ H ₆ )Cl ₂ (C ₄ H ₈ O) ₂ ] into a Schlenk flask, ether was slowly added dropwise at -78 °C and stirred at room temperature for one day. Thereafter, after filtering the red reaction solution, 4 equivalents of HCl ether solution (1 M) was slowly added dropwise at -78 °C, followed by stirring at room temperature for 3 hours. Thereafter, the mixture was filtered and vacuum dried to obtain an ansa-metallocene compound as an orange solid 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 condensated through cracking at 150 ° C to extract cyclopentadiene (1 equiv), dissolved in THF (0.3 M), slowly added n-BuLi (1.05 eq) dropwise at -25 ° C, and stirred at room temperature for 3 hours. . Thereafter, dichlorodimethylsilane (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. After adding CuCN (2 mol%) and stirring for 30 minutes, a mono-Si solution as the first reactant was added. Thereafter, the mixture was stirred at room temperature overnight, worked up using water, and dried to obtain a ligand.

Preparation of the 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. In a separate flask, a slurry prepared by mixing ZrCl ₄ (1 eq) with toluene (0.17 M) was prepared, added to the ligand solution, and then stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum-dried, dichloromethane was reintroduced to remove LiCl through a filter, etc., and the filtrate was vacuum-dried and recrystallized at room temperature by adding dichloromethane/hexane. Then, the resulting solid was filtered and vacuum dried 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>

Preparation 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 using a cannula. Toluene (400 mL) was added, stirred for 1 minute, left for 15 minutes, and the solvent was decanted using a cannula.

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

A supported catalyst was obtained by first drying at room temperature for 5 hours under vacuum and secondarily drying at 45 °C for 4 hours under vacuum.

Preparation Examples 2 to 12

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 instead of the metallocene compound of Synthesis Example 1.

Comparative Preparation Examples 1 to 6

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 instead of the metallocene compound of Synthesis Example 1.

<Preparation of Propylene-Ethylene Random Copolymer>

Example 1

In the presence of the silica-supported metallocene catalyst prepared in Preparation Example 1, bulk propylene and ethylene-slurry polymerization was performed using two consecutive 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 8 minutes or more, 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 injected was about 150 ppm based on the propylene content continuously introduced. In addition, ethylene (C2) was directly injected into the loop reactor so as to be 3.5 wt% based on the content of propylene (C3) continuously introduced, and a bulk-slurry polymerization process was performed.

Examples 2 to 12

Except for using the silica-supported metallocene catalysts of Preparation Examples 2 to 12, respectively, instead of the silica-supported metallocene catalyst of Preparation Example 1, propylene and ethylene bulk-slurry polymerization was carried out in the same manner as in Example 1 did

Comparative Example 1

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

Comparative Example 2

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

Comparative Example 3

A Ziegler-Natta (Z/N) catalyst (manufacturer: Lyondellbasell, product name: ZN127VS) was used instead of a metallocene catalyst, and the amount of ethylene (C2) was changed to 3.0 wt% based on the propylene (C3) content. Except for the bulk-slurry polymerization of propylene and ethylene was carried out 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 amount of ethylene (C2) was changed to 2.0 wt% based on the propylene (C3) content. Bulk-slurry polymerization of propylene and ethylene was carried out by the method.

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 amount of ethylene (C2) was changed to be 2.5 wt% based on the content of propylene (C3).

Comparative Example 6

Propylene and ethylene were prepared in the same manner as in Comparative Example 4, except that the ethylene (C2) input amount was changed to 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 amount of ethylene (C2) was changed to 3.0 wt% based on the propylene (C3) content. Bulk-slurry polymerization of propylene and ethylene was carried out by the method.

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 4.5 wt% based on the content of propylene (C3).

Comparative Example 9

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

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 amount of ethylene (C2) was changed to 5.5 wt% based on the propylene (C3) content. Bulk-slurry polymerization of propylene and ethylene was carried out by the method.

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 amount of ethylene (C2) was changed to 4.5 wt% based on the propylene (C3) content. Bulk-slurry polymerization of propylene and ethylene was carried out by the method.

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 ethylene (C2) input was changed to 2.0 wt% based on the propylene (C3) content. Bulk-slurry polymerization of propylene and ethylene was carried out by the method.

<Experimental example>

Property evaluation of propylene-ethylene random copolymer

Properties of the propylene-ethylene random copolymers prepared in Examples and Comparative Examples were evaluated by the following methods.

(1) Comonomer content (C2, wt%)

According to ASTM D 5576 of the American Society for Testing and Materials, a film or film-type specimen of propylene-ethylene random copolymer is fixed to the magnetic holder of the FT-IR equipment, and then the IR absorption spectrum reflects the specimen thickness of 4800 ~ 3500 cm ^{- 1} The area of the 710 ~ 760 cm ^-1 peak where the ethylene component of the peak appears is measured, and the measured value is divided by the area of the 710 ~ 760 cm ^-1 peak of the standard sample by the peak height of 4800 ~ 3500 cm ^-1 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 was heated to 200 ° C., maintained at that temperature for 5 minutes, then lowered to 30 ° C., and then increased again to determine the peak of the DSC (Differential Scanning Calorimeter, manufactured by TA) curve as the melting point (Tm). , and when the temperature was lowered to 30 ° C., the peak of the curve was measured as the crystallization temperature (Tc). At this time, the rate of temperature rise and fall was 10 °C/min, and the melting point (Tm) and crystallization temperature (Tc) were measured in the second temperature rising and falling section.

(3) Melt index (MI)

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

(4) Haze (%)

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

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

Each sample of the propylene-ethylene random copolymer was pretreated by adding xylene, heating at 135° C. for 1 hour, and cooling for 30 minutes. In OminiSec (Viscotek's FIPA) equipment, xylene was flowed for 4 hours at a flow rate of 1 mL/min, and RI (Refractive Index), DP (Pressure across middle of bridge), IP (Inlet pressure through bridge top) When the base line of the bottom was stabilized, the concentration of the pretreated sample and the amount of injection were measured, and then the peak area was calculated.

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

According to the VDA 277 method, total volatile organic compound (TVOC) emissions (TVOC, Total Volatile Organic Compound, ppm) contained in the propylene-ethylene random copolymer were measured using a Headspace-GC (Gas chromatography) apparatus.

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

polymerization process Properties of Copolymer catalyst C2
input
(wt%) C2 content
(IR analysis wt%) Tm
(℃) Random Tc
(℃) MI
(g/10min) Haze
(%) XS
(wt%) TVOC (ppm) Example 1 Preparation Example 1 3.5 4.3 125.2 73.0 18.8 7.1 0.6 58 Example 2 Preparation Example 2 3.5 4.2 126.2 73.8 19.1 7.2 0.7 55 Example 3 Preparation Example 3 3.5 4.3 125.4 72.5 19.1 7.1 0.8 55 Example 4 Production Example 4 3.5 4.2 125.4 72.6 19.2 7.3 0.6 58 Example 5 Preparation Example 5 3.5 4.2 125.5 72.8 19.5 7.2 0.7 55 Example 6 Preparation Example 6 3.5 4.2 125.3 72.8 18.5 7.2 0.8 58 Example 7 Preparation Example 7 3.5 4.1 125.3 73.5 18.4 7.4 0.6 58 Example 8 Preparation Example 8 3.5 4.2 125.4 73.1 18.4 7.3 0.8 57 Example 9 Preparation Example 9 3.5 4.2 125.2 73.2 18.6 7.3 0.7 56 Example 10 Preparation Example 10 3.5 4.2 125.1 73.0 18.6 7.2 0.7 57 Example 11 Preparation Example 11 3.5 4.3 125.8 72.8 18.4 7.1 0.7 55 Example 12 Preparation Example 12 3.5 4.2 125.6 73.8 18.5 7.2 0.8 58 Comparative Example 1 Preparation Example 1 2.0 2.6 134.6 85.5 18.1 8.3 0.8 54 Comparative Example 2 Preparation 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 comparison
Preparation Example 1 2.0 2.3 131.1 83.1 18.4 8.5 0.6 56 Comparative Example 5 comparison
Preparation Example 1 2.5 2.8 125.8 73.5 19.3 8.1 0.6 61 Comparative Example 6 comparison
Preparation Example 1 3.5 measurement
not possible measurement
not allowed measurement
not allowed measurement
not allowed measurement
not possible measurement
not allowed measurement
not possible Comparative Example 7 comparison
Preparation Example 2 3.0 2 132.1 83.8 19.1 8.8 0.8 58 Comparative Example 8 comparison
Preparation Example 2 4.5 2.8 126.1 74.5 20 8.2 0.6 56 Comparative Example 9 comparison
Preparation Example 2 6.0 measurement
not allowed measurement
not allowed measurement
not possible measurement
not allowed measurement
not possible measurement
not allowed measurement
not possible Comparative Example 10 comparison
Preparation Example 3 6.0 3.5 126.1 78.1 18.2 7.8 0.6 56 Comparative Example 11 comparison
Production Example 4 5.5 3.3 125.8 77.1 19.6 7.7 0.7 50 Comparative Example 12 comparison
Preparation Example 5 4.5 2.6 125.7 76.8 20.1 8.3 1.1 54 Comparative Example 13 comparison
Preparation Example 6 2.0 measurement
not allowed measurement
not possible measurement
not allowed measurement
not allowed measurement
not possible measurement
not possible measurement
not possible

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 ( It was confirmed that not only can the C2) content be increased, but the increased ethylene (C2) content exhibits a characteristic of lowering crystallinity, and through this, transparency is improved. In addition, in the case of Examples 1 to 12, it can be seen that eco-friendliness can be secured as a high-transparency propylene-ethylene random copolymer for injection used in food containers and the like because the TVOC is remarkably low.

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

In addition, in Comparative Example 3 using a Ziegler-Natta (Z/N) catalyst, despite the high ethylene (C2) content, the blocky and non-uniform copolymerization of ethylene (C2) in the polymer structure has a crystallization temperature (Tc ) was very high as 111 ℃, TVOC was extremely high as 310 ppm, and the atactic xylene soluble content (X.S, Xylene soluble) was also confirmed to be very high as 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 that does not contain an indacene ligand and contains a generally known cyclopentadienyl, in the case of maintaining the Tm range in which fouling does not occur, There was a limit to increasing the ethylene (C2) content, so it could not reach a certain level of transparency. In particular, in the case of Comparative Example 6, fouling occurred during the polymerization process, and the physical properties of the copolymer could not be evaluated.

Likewise, in the case of Comparative Examples 7 to 9 using the catalyst composition of Comparative Preparation Example 2 containing a metallocene compound in which an indene ligand is bridged instead of a cyclopentadienyl (Cp) ligand bridged with an indacene ligand, basically Since the Tm itself of homopolypropylene is low, fouling occurs when the ethylene (C2) content is increased, and thus the ethylene (C2) content cannot be maintained at a certain level. Moreover, since the reactivity of ethylene (C2) is not good, the input amount of ethylene (C2) 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 during the polymerization process, and physical properties of the copolymer could not be evaluated.

In addition, in the case of Comparative Examples 10 to 12 using a catalyst composition containing a metallocene compound having a bisindenyl (or indacenyl) group, the ethylene conversion rate (C2 conversion) is very low, so the amount of ethylene (C2) injected must be high for copolymerization. It was possible to raise the ethylene (C2) content in the body to a certain level or higher, but this also had limitations in increasing the ethylene (C2) content, so it could not reach a certain level of transparency.

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, which gives polypropylene directionality, and the physical properties of the copolymer could not be evaluated.

Claims (11)

The melting point (Tm) is 125 ° C or higher,
The content of ethylene is 4.0% by weight or more;
The crystallization temperature (Tc) is 75 ° C or less,
Melt index (MI _2.16 , melt index measured at 230 ° C., 2.16 kg load) of 16 g / min to 22 g / min,
Propylene-ethylene random copolymer.
According to claim 1,
The melting point (Tm) is 125 ° C to 150 ° C,
Propylene-ethylene random copolymer.
According to claim 1,
The content of ethylene is 4.0% to 5.5% by weight,
Propylene-ethylene random copolymer.
According to claim 1,
The crystallization temperature (Tc) is 65 ° C to 75 ° C,
Propylene-ethylene random copolymer.
According to claim 1,
Xylene soluble content (XS, Xylene soluble) is 1.0% by weight or less,
Propylene-ethylene random copolymer.
According to claim 1,
Haze (Haze) measured according to the ASTM 1003 method is 7.5% or less,
Propylene-ethylene random copolymer.
According to claim 1,
Total volatile organic compound emission (TVOC) measured according to the VDA 277 method is 70 ppm or less,
Propylene-ethylene random copolymer.
According to 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 copolymers:
[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 are each independently a halogen element;
R ¹ and R ² are the same as or different from each other, and are 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 represents C _1-20 alkyl;
R ⁷ is a substituted or unsubstituted C _6-20 aryl;
R ⁸ is C _1-20 alkyl.
According to 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, C _1-6 straight or branched chain alkyl substituted phenyl, naphthyl, or C _1-6 straight or branched chain alkyl substituted naphthyl;
R ⁸ is C _1-6 straight or branched chain alkyl;
Propylene-ethylene random copolymer.
According to claim 8,
The metallocene compound is represented by Formula 1-1 below,
Propylene-ethylene random copolymers:
[Formula 1-1]

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

.