阅读说明：本技术 丙烯-乙烯无规共聚物 (Propylene-ethylene random copolymer ) 是由 金炳奭 李仁羡 金祏焕 李定鋺 权桐贤 金世英 朴喜广 芮志和 于 2020-06-11 设计创作，主要内容包括：本发明涉及一种用于高透明度注射的丙烯-乙烯无规共聚物,该共聚物在具有低的总挥发性有机化合物排放(TVOC)的同时具有优异的可加工性,并且具有最大化的乙烯含量。(The present invention relates to a propylene-ethylene random copolymer for high transparency injection having excellent processability while having low total volatile organic compound emission (TVOC) and maximized ethylene content.)

1. A propylene-ethylene random copolymer, wherein the copolymer has

A melting point (Tm) of 125 ℃ or higher,

an ethylene content of 4.0% by weight or more,

a crystallization temperature (Tc) of 75 ℃ or less, and

melt Index (MI)_2.16Melt index, measured at 230 ℃ under a 2.16kg load) of 16g/min to 22 g/min.

2. The propylene-ethylene random copolymer according to claim 1, wherein the melting point (Tm) is from 125 ℃ to 150 ℃.

3. The propylene-ethylene random copolymer according to claim 1, wherein the ethylene content is from 4.0 to 5.5% by weight.

4. The propylene-ethylene random copolymer according to claim 1, wherein the crystallization temperature (Tc) is from 65 ℃ to 75 ℃.

5. Propylene-ethylene random copolymer according to claim 1, wherein the xylene solubles content (X.S) is 1.0 wt% or less.

6. The propylene-ethylene random copolymer according to claim 1, wherein the haze is 7.5% or less as measured according to the American society for testing and materials ASTM 1003.

7. The propylene-ethylene random copolymer of claim 1, wherein the Total Volatile Organic Compounds (TVOC) emission measured according to VDA 277 method is 70ppm or less.

8. The propylene-ethylene random copolymer of claim 1, wherein the propylene-ethylene random copolymer is prepared by copolymerizing a propylene monomer and an ethylene comonomer in the presence of a catalyst composition comprising a metallocene compound of the following chemical formula 1:

[ chemical formula 1]

In the chemical formula 1, the metal oxide is represented by,

m is a group 4 transition metal,

X¹and X²Are identical to or different from one another and are each independently halogen,

R¹and R²Are identical to or different from each other and are each independently C_1-20Alkyl radical, C_2-20Alkenyl radical, C_2-20Alkoxyalkyl group, C_6-20Aryl radical, C_7-40Alkylaryl or C_7-40An arylalkyl group, which is a cyclic alkyl group,

R³to R⁶Are identical to or different from each other and are each independently C_1-20An alkyl group, a carboxyl group,

R⁷is substituted or unsubstituted C_6-20Aryl radical, and

R⁸is C_1-20An alkyl group.

9. The propylene-ethylene random copolymer according to claim 8, wherein

R¹And R²Each independently is C_1-8Straight or branched alkyl, or C_2-12A straight-chain or branched-chain alkoxyalkyl group,

R³to R⁶Each independently is C_1-6A linear or branched alkyl group,

m is a zirconium or a hafnium compound,

R⁷is phenyl, substituted by C_1-6Phenyl, naphthyl or substituted by C, of straight-chain or branched alkyl groups_1-6Naphthyl of a straight or branched alkyl group, and

R⁸is C_1-6Straight or branched chain alkyl.

10. The propylene-ethylene random copolymer of claim 8, wherein the metallocene compound is represented by the following chemical formula 1-1:

[ chemical formula 1-1]

In the chemical formula 1-1, the metal oxide,

M、X¹、X²、R¹、R²and R⁷As defined in claim 8.

11. The propylene-ethylene random copolymer of claim 8, wherein the metallocene compound is any one of compounds represented by the following chemical formula:

Technical Field

Cross Reference to Related Applications

The present disclosure is based on and claims priority from korean patent application nos. 10-2019-0068772 and 10-2020-0070125, filed on 11/6/2020/6/10/2019, respectively, the disclosures of which are hereby incorporated by reference in their entirety.

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

Background

Polypropylene resin is a general-purpose resin which is easy to process and has excellent cost properties, and thus has wide applications, precisely replacing conventional materials such as glass, wood, paper, metal, and the like, and can be applied even to the field of other plastic products including engineering plastics.

Recently, a method of random copolymerization or terpolymerization of propylene with ethylene or butene has been studied for producing injection-molded articles requiring transparency. Among them, it is known that propylene having a higher ethylene content is more effective as a maximum transparency factor. However, the crystallinity of randomly copolymerized polypropylene decreases with increasing ethylene (comonomer of the polymer) content, as compared to conventional homo-polypropylene. Therefore, in the random copolymerized polypropylene, a balance between rigidity and impact strength cannot be maintained, or it is difficult to secure processing stability.

On the other hand, polypropylene polymerization catalysts are mainly classified into Ziegler-Natta type catalysts and metallocene type catalysts. Since the Ziegler-Natta catalyst is a multi-site catalyst in which a plurality of active sites are mixed, it is characterized by a broad molecular weight distribution. Further, in the case of using a Ziegler-Natta catalyst, there is a problem in that there is a limit in securing desired physical properties due to non-uniform composition distribution of comonomers. In particular, when random copolymerization with ethylene is performed in the presence of a Ziegler-Natta catalyst (Z/N, Ziegler-Natta) to secure transparency, polymerizability of ethylene is very high, and thus it is a heterogeneous polymer, i.e., a polymer in which an ethylene polymer is formed as blocks between propylene polymers, not a repeating structure. Therefore, in the case of using a Ziegler-Natta catalyst for random copolymerization of ethylene, physical properties are greatly reduced, and there is a problem in that emission of Volatile Organic Compounds (VOCs) is high.

However, the metallocene catalyst comprises a combination of a main catalyst having a transition metal compound as a main component and a co-catalyst having an organometallic compound having aluminum as a main component. This catalyst is a single-site catalyst, which is a homogeneous composite catalyst, and due to the single-site nature, provides polymers with narrow molecular weight distribution and uniform comonomer composition distribution. In addition, by varying the ligand structure of the catalyst and the polymerization conditions, various properties associated with the resulting polymer, such as stereoregularity, copolymerization properties, molecular weight, or crystallinity, can be controlled.

In particular, products using Ziegler-Natta catalysts are the predominant products for various commercial polypropylenes. Recently, due to changes in environmental awareness, many product groups have sought to reduce the production of Volatile Organic Compounds (VOCs). Therefore, as an eco-friendly material for food containers, the conversion to polypropylene resin products (using metallocene catalysts having low odor and low elution properties) is being accelerated.

However, when polypropylene is produced using a conventional metallocene catalyst, the melting point of polypropylene produced using a conventional metallocene catalyst is lower than that of polypropylene produced using a Ziegler-Natta catalyst. Thus, in the case of using the conventional metallocene catalyst, there is a limit to increase the ethylene content as a comonomer. Therefore, in the injection product, it is difficult to achieve high transparency while reducing crystallinity.

Therefore, there is a need to develop a method for producing high transparency polypropylene for injection products by maximizing ethylene content and achieving low total volatile organic compound emission (TVOC) using a metallocene-based catalyst.

Disclosure of Invention

Technical problem

In the present disclosure, a propylene-ethylene random copolymer for high transparency injection is provided that uses high comonomer content while producing low total volatile organic compound emissions (TVOC).

Technical scheme

In the present disclosure, there is provided a propylene-ethylene random copolymer satisfying the following conditions: a melting point (Tm) of 125 ℃ or more, an ethylene content of 4.0% by weight or more, a crystallization temperature (Tc) of 75 ℃ or less, and a Melt Index (MI)_2.16Melt index, measured at 230 ℃ under a 2.16kg load) of 16g/min to 22 g/min.

The propylene-ethylene random copolymer may have a melting point (Tm) of 125 to 150 ℃, an ethylene content of 4.0 to 5.5 wt%, and a crystallization temperature (Tc) of 65 to 75 ℃.

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

Further, the propylene-ethylene random copolymer may have a haze of 7.5% or less as measured according to the american society for testing and materials ASTM 1003 method, and a total volatile organic compound emission (TVOC) of 70ppm or less as 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 comprising a metallocene compound of the following chemical formula 1:

[ chemical formula 1]

In the chemical formula 1, the metal oxide is represented by,

m is a group 4 transition metal,

X¹and X²Are identical to or different from one another and are each independently halogen,

R¹and R²Are identical to or different from each other and are each independently C_1-20Alkyl radical, C_2-20Alkenyl radical, C_2-20Alkoxyalkyl group, C_6-20Aryl radical, C_7-40Alkylaryl or C_7-40An arylalkyl group, which is a cyclic alkyl group,

R³to R⁶Are identical to or different from each other and are each independently C_1-20An alkyl group, a carboxyl group,

R⁷is substituted or unsubstituted C_6-20Aryl radical, and

R⁸is C_1-20An alkyl group.

Here, in chemical formula 1, R¹And R²May each independently be C_1-8Straight or branched alkyl, or C_2-12Straight or branched alkoxyalkyl. In particular, R¹And R²And may be, independently of one another, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl or tert-butoxyhexyl.

In chemical formula 1, R³To R⁶May each independently be C_1-6Straight or branched alkyl, or C_1-3Straight or branched chain alkyl. In particular, R³To R⁶Each independently may be methyl, ethyl, propyl or isopropyl, preferably methyl.

Further, in chemical formula 1, M may preferably be zirconium (Zr) or hafnium (Hf).

In chemical formula 1, R⁷May be phenyl, substituted by C_1-6Phenyl, naphthyl or substituted by C, of straight-chain or branched alkyl groups_1-6Naphthyl of straight or branched alkyl. In particular toIn the sense that R⁷One or two or more of the phenyl or naphthyl groups of (a) may be substituted by C_1-6Linear or branched alkyl. For example, R⁷One or two or more hydrogens of the phenyl or naphthyl group of (a) may be substituted with a methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl group, respectively.

Further, in chemical formula 1, R⁸May be C_1-6Straight or branched alkyl, or C_1-3Straight or branched chain alkyl. In particular, R⁸It may be methyl, ethyl, or propyl, or isopropyl, with methyl being preferred.

Specifically, the metallocene compound of chemical formula 1 may be preferably represented by the following chemical formula 1-1:

[ chemical formula 1-1]

In the chemical formula 1-1, the metal oxide,

M、X¹、X²、R¹、R²and R⁷As defined in chemical formula 1.

For example, the metallocene compound represented by chemical formula 1 may be any one of compounds represented by the following structural formulae. The following structural formulae are shown by way of example and will be described in detail. However, it is not intended to be limited to the particular forms disclosed.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

The singular forms also include the plural forms unless the context clearly dictates otherwise.

It will be further understood that the terms "comprises," "comprising," "has," "having" or "having" specify the presence of stated features, integers, steps, components, or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components, or groups thereof.

Further, as used herein, where a layer or element is referred to as being "formed" on another layer or element, it is meant that the layer or element is formed directly on the other layer or element, or that the other layer or element may be additionally formed between layers, on a body, or on a substrate.

While the invention is amenable to various modifications and alternative forms, specifics thereof have been shown by way of example in the drawings and will be described in detail. However, it is not intended to limit the invention to the particular forms disclosed, and it should be understood that the invention includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the present invention will be described in detail.

According to one aspect of the present disclosure, a propylene-ethylene random copolymer is characterized by satisfying the following conditions: a melting point (Tm) of 125 ℃ or more, an ethylene content of 4.0% by weight or more, a crystallization temperature (Tc) of 75 ℃ or less, and a Melt Index (MI)_2.16Melt index, measured at 230 ℃ under a 2.16kg load) of 16g/min to 22 g/min.

Propylene (co) polymers prepared by Ziegler-Natta catalysts have a problem that volatile organic compound emissions (VOCs) are high and rigidity is greatly reduced due to the reduction of crystalline properties. In addition, since the melting point of the polymer is low and fouling occurs during polymerization when using a conventional metallocene catalyst, increasing the ethylene content as a comonomer is limited. Therefore, it is necessary to increase the ethylene content to maintain high transparency and improve processability to be suitable for injection molding.

Thus, according to the present disclosure, it is possible to provide a propylene-ethylene random copolymer for preparing a high transparency injection product, which has high rigidity, excellent processability, and low total volatile organic compound emission (TVOC).

In particular, the present disclosure provides a random copolymerized polypropylene, in particular a propylene-ethylene random copolymer comprising ethylene as a comonomer. On the other hand, in the case of a random copolymer using butene as a comonomer instead of ethylene or a terpolymer using butene and ethylene as comonomers, the haze value was not good. Therefore, unlike the resin composition of the present disclosure, a random copolymer including butene as a comonomer is difficult to prepare a high transparency resin for injection.

The propylene-ethylene random copolymer according to an embodiment of the present disclosure is characterized in that the content of ethylene at a melting point (Tm) of 120 ℃ or more is 4.0% by weight or more. In particular, the propylene-ethylene random copolymer of the present disclosure can be prepared by using a metallocene catalyst having a novel structure as described below. Accordingly, the propylene-ethylene random copolymer of the present disclosure can ensure a very high melting point in the homo-polypropylene resin and high copolymerizability with ethylene. Thus, even with such a high ethylene content, the propylene-ethylene random copolymer of the present disclosure maintains a high melting point.

Specifically, the propylene-ethylene random copolymer according to the embodiments of the present disclosure may have a melting point (Tm) of 125 ℃ or more, or 125 ℃ to 150 ℃. By having such a high melting point, a fouling phenomenon does not occur during polymerization, 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 ℃ or higher, or 125.1 ℃ to 150 ℃.

In addition, the propylene-ethylene random copolymer may have a crystallization temperature (Tc) of 75 ℃ or less, or 65 ℃ to 75 ℃. Since the crystallinity is reduced due to such a low crystallinity temperature, it has a low haze value and can ensure high transparency when applied to an injection product such as a film. More specifically, the propylene-ethylene random copolymer may have a crystallization temperature (Tc) of 74.5 ℃ or less, or 65 ℃ to 74.5 ℃; or 74 ℃ or less, or 68 ℃ to 74 ℃; or 74 ℃ or less, or 70 ℃ to 73.8 ℃.

In the present disclosure, the melting point (Tm) and the crystallization temperature (Tc) can be measured using a differential scanning calorimeter (DSC, apparatus name: DSC 2920, manufacturer: TA instrument). In detail, the polypropylene polymer is heated to 200 ℃ by increasing the temperature, then held at this temperature for 5 minutes, after which the temperature is reduced to 30 ℃. Then, the temperature was increased again, and the temperature corresponding to the peak in the DSC (differential scanning calorimeter, manufactured by TA) curve was determined as the melting point (Tm). Thereafter, when the temperature was again decreased to 30 ℃, the top of the curve was taken as the crystallization temperature (Tc). In this regard, the temperature is increased and decreased at a rate of 10 deg.C/min, respectively, and the melting point (Tm) and crystallization temperature (Tc) are the results measured at the second temperature increase and decrease sections.

In addition, in the propylene-ethylene random copolymer according to an embodiment of the present disclosure, as described above, the ethylene content at a melting point (Tm) of 125 ℃ or more may be 4.0 wt% or more, or 4.0 wt% to 5.5 wt%. As described above, by maintaining a high melting point and increasing the ethylene content, it has a low haze value and can ensure 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% by weight or more, or 4.1% by weight to 5.5% by weight; or 4.2 wt% or more, or 4.2 wt% to 5.5 wt%.

Generally, when a propylene-ethylene random copolymer is prepared using comonomers in a conventional manner, heterogeneous comonomers are incorporated between main chains, thereby changing the layered structure of the resin. As a result, the melting point (Tm) of the conventional propylene-ethylene random copolymer is lowered, it is difficult to maintain the balance between rigidity and impact strength, and to ensure process stability. In contrast, in the present disclosure, by using a metallocene catalyst having a novel structure as described below, a very high melting point in the case of a homo-polypropylene resin can be ensured, and high copolymerizability with ethylene can be achieved. Therefore, even with a high ethylene content as described above, the propylene-ethylene random copolymer of the present disclosure can exhibit improved physical properties while maintaining a high melting point of 125 ℃ or more.

Meanwhile, in the present disclosure, the comonomer content in the propylene-ethylene random copolymer may be measured according to the U.S. testAnd materials association ASTM D5576 as follows: fixing the film or film sample of propylene random copolymer on the magnetic support of FT-IR instrument, and measuring the infrared absorption spectrum at 4800cm^-1To 3500cm^-1The peak height in which the thickness of the sample is reflected, and 710cm^-1To 760cm^-1Indicates the peak area of the ethylene component, and then the measurement value is substituted into the calibration equation (710 cm of the standard sample^-1To 760cm^-1Area of the peak in (1) divided by 4800cm^-1To 3500cm^-1Plotted against the value obtained for peak height in (1).

On the other hand, according to ASTM D1238, the melt index MI of the propylene-ethylene random copolymer of the embodiments of the present disclosure is measured at 230 ℃ under a load of 2.16kg_2.16From about 16g/min to about 22 g/min. By optimizing the melt index range as above, a highly transparent product can be obtained while maintaining excellent processability during injection molding. More specifically, the propylene-ethylene random copolymers of the present disclosure may have a Melt Index (MI)_2.16) From about 17g/10min to about 21g/10min, or from about 18g/10min to about 20g/10 min. In particular, when the Melt Index (MI) of the propylene-ethylene random copolymer_2.16) When the amount is less than about 16g/10min, the workability is poor, the injection pressure is increased, and the injection molding is difficult. In contrast, when the Melt Index (MI) of the propylene-ethylene random copolymer_2.16) Above about 22g/10min, it cannot be used as an injection resin because the viscosity is too low to flow down and cannot be injected.

As described above, unlike polypropylene prepared using a conventional Ziegler-Natta catalyst or a conventional metallocene catalyst, the propylene-ethylene random copolymer of the present disclosure maintains a high ethylene content of 4.0 wt% or more, a melting point (Tm) of 125 ℃ or more, and ensures a low crystallization temperature (Tc) of 75 ℃ or less and an optimized Melt Index (MI) of 16g/10min to 22g/10min_2.16Melt index measured at 230 ℃ under a load of 2.16 kg). Accordingly, the propylene-ethylene random copolymer of the present disclosure can ensure excellent processability during polymerization and injection molding. In addition, according to the propylene-ethylene random copolymer of the present disclosure, total volatile organic compound emission (TVOC) is low, andand can exhibit high rigidity and high transparency.

For example, in the propylene-ethylene random copolymer according to an embodiment of the present disclosure, the xylene solubles content (XS) may be about 1.0 wt% or less, or about 0.85 wt% or less, or about 0.7 wt% or less. The xylene solubles content is a value representing the content of the random component in the whole copolymer. This means that, as described above, the lower the xylene solubles content, the lower the viscosity of the propylene-ethylene random copolymer. This is an advantage that can be ensured when polymerization is carried out using a metallocene catalyst. Therefore, the propylene-ethylene random copolymer according to the present disclosure is characterized in that, since the content of xylene dissolved is low, the possibility of occurrence of process defects during processing and heat-sealing is very low.

In addition, the propylene-ethylene random copolymer has a haze of about 7.5% or less, or about 7.3% or less, or about 7.2% or less, as measured according to the American society for testing and materials ASTM 1003 method, indicating high transparency.

The propylene-ethylene random copolymer has a total volatile organic compound emission (TVOC) of about 70ppm or less, or about 65ppm or less, or about 60ppm or less, as determined by the VDA 277 method. By having such a low total volatile organic compound emission (TVOC), it is possible to ensure eco-friendliness of the propylene-ethylene random copolymer as a transparent injection product for use in food containers and the like.

As described above, the propylene-ethylene random copolymer of the present disclosure can ensure high rigidity and excellent transparency as well as superior process stability and processability, compared to polypropylene prepared using a conventional Ziegler-Natta catalyst or a conventional metallocene catalyst.

Meanwhile, the propylene random copolymer having the above-described physical properties and structural features according to an embodiment of the present disclosure may be prepared by copolymerizing a propylene monomer and an ethylene comonomer in the presence of a catalyst composition (including the metallocene compound of the following chemical formula 1 as a catalytically active ingredient):

[ chemical formula 1]

In the chemical formula 1, the metal oxide is represented by,

m is a group 4 transition metal,

X¹and X²Are identical to or different from one another and are each independently halogen,

R¹and R²Are identical to or different from each other and are each independently C_1-20Alkyl radical, C_2-20Alkenyl radical, C_2-20Alkoxyalkyl group, C_6-20Aryl radical, C_7-40Alkylaryl or C_7-40An arylalkyl group, which is a cyclic alkyl group,

R³to R⁶Are identical to or different from each other and are each independently C_1-20An alkyl group, a carboxyl group,

R⁷is substituted or unsubstituted C_6-20Aryl radical, and

R⁸is C_1-20An alkyl group.

Unless otherwise specified herein, the following terms may be defined as follows.

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

C_1-20The alkyl group may be a linear, branched or cyclic alkyl group. Specifically, C_1-20The alkyl group may be C_1-20A linear alkyl group; c_1-15A linear alkyl group; c_1-5A linear alkyl group; c_3-20A branched or cyclic alkyl group; c_3-15A branched or cyclic alkyl group; or C_3-10A branched or cyclic alkyl group. More specifically, C_1-20The alkyl group may be, but is not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.

C_2-20The alkenyl group may be a linear, branched or cyclic alkenyl group. Specifically, it may be allyl, vinyl, propenyl, butenyl, pentenyl, etc., but is not limited thereto.

C_1-20The alkoxy group may be methoxy, ethoxy, or,Isopropoxy, n-butoxy, tert-butoxy, pentoxy, cyclohexoxy and the like, but not limited thereto.

C_2-20The alkoxyalkyl group is a functional group in which at least one hydrogen of the above alkyl group is substituted by an alkoxy group, and may be an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an isopropoxymethyl group, an isopropoxyethyl group, an isopropoxypropyl group, an isopropoxyhexyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, a tert-butoxypropyl group, and a tert-butoxyhexyl group; aryloxyalkyl, such as phenoxyhexyl; and the like, but are not limited thereto.

C_1-20Alkylsilyl or C_1-20The alkoxysilyl group being-SiH₃A functional group in which 1 to 3 hydrogens of (a) are substituted with the above-mentioned 1 to 3 alkyl or alkoxy groups, which may be alkylsilyl groups such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl or dimethylpropylsilyl; an alkoxysilyl group such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group or a dimethoxyethoxysilyl group; or an alkoxyalkyl silyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, a dimethoxypropylsilyl group; and the like, but are not limited thereto.

C_1-20Silylalkyl is a functional group in which at least one hydrogen of the above alkyl group is replaced by a silyl group, which can be-CH₂-SiH₃Methylsilylmethyl or dimethylethoxysilylpropyl, and the like, but is not limited thereto.

In addition, C_1-20The alkylene group is the same as the above alkyl group except that it is a divalent substituent which may be methylene, ethylene, propylene, butene, pentene, hexene, heptene, octene, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, etc., but is not limited thereto.

C_6-20The aryl group may be a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. E.g. C_6-20The aryl group may be phenyl, biphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, etc.,but is not limited thereto.

C_7-20Alkylaryl may refer to a substituent wherein at least one hydrogen of the aromatic ring is substituted with an alkyl group as described above. E.g. C_7-20The alkylaryl group may be a methylphenyl group, an ethylphenyl group, a methylbiphenyl group, a methylnaphthalene group, etc., but is not limited thereto.

C_7-20Arylalkyl may refer to a substituent wherein at least one hydrogen of the alkyl group is replaced with an aryl group as described above. E.g. C_7-20The arylalkyl group may be a phenylmethyl group, a phenylethyl group, a biphenylmethyl group, a naphthylmethyl group, etc., but is not limited thereto.

In addition, C_6-20The arylene group is the same as the above-mentioned aryl group except that it is a divalent substituent which may be a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, a phenanthrenylene group, a fluorenylene group or the like, but is not limited thereto.

The group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf) or(Rf) may specifically be titanium (Ti), zirconium (Zr) or hafnium (Hf). More specifically, it may be zirconium (Zr) or hafnium (Hf), but the present disclosure is not limited thereto.

Further, 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), but the disclosure is not limited thereto.

The above substituents may be optionally substituted with one or more substituents selected from the group consisting of: a hydroxyl group; halogen; alkyl or alkenyl, aryl, alkoxy groups; alkyl or alkenyl, aryl, alkoxy groups comprising at least one group 14 to group 16 heteroatom; a silyl group; an alkylsilyl or alkoxysilyl group; a phosphine group; a phosphide group; a sulfonate group; and a sulfone group.

The catalyst composition for preparing a propylene-ethylene random copolymer according to an embodiment of the present invention includes the compound of chemical formula 1 as a single metallocene catalyst. Thus, the molecular weight distribution of the propylene-ethylene random copolymers of the present disclosure can be significantly narrower than that of propylene copolymers prepared in a conventional manner using a mixture with two or more catalysts. Therefore, the rigidity of the propylene-ethylene random copolymer of the present disclosure can be improved.

Meanwhile, the metallocene compound has an asymmetric structure in which cyclopentadienyl-based groups different from each other are connected as a ligand through a bridge, as shown in chemical formula 1 above.

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

According to the specific structure described above, the metallocene compound may have various characteristics of two different cyclopentadienyl-based rings, or may selectively utilize these advantages, thereby exhibiting better catalytic activity.

In particular, since the hydrogen functional group is substituted with an alkyl group in the cyclopentadienyl structure, the cyclopentadienyl structure plays an important role in maintaining the tacticity which is very important for propylene polymerization. Maintaining the steric arrangement during the preparation of polypropylene can induce growth when the isotactic polymer remains highly active. In the case of cyclopentadienyl (Cp) substituted only by hydrogen, there is no bulky moiety. Thus, when propylene is inserted, the catalyst is in a fully open state, and thus the tacticity collapses to form atactic polypropylene (atactic PP).

In addition, when propylene (C3) and H₂When reacted together, the reaction is competitive. When the 2-position of the indacenyl structure of the ligand of chemical formula 1 is substituted with a structure, for example, when R⁸Quilt C_1-20When alkyl substituted, a specific spatial arrangement is imparted to the metal center, thus improving the degree of C or less₃H of (A) to (B)₂The reactivity of (a). Thus, when R is in the 2-position of the indacenyl structure⁸Substituted by C_1-20Alkyl groups, such as methyl, can increase the hydrogen reactivity during polymerization.

In addition, an aryl substituent capable of giving a large amount of electrons is substituted at the 4-position in the indacenyl structure, and thus electrons are given in a large amount to the metal atom contained in the bridge structure of chemical formula 1, thereby generatingHigher catalytic activity. As used herein, an example of an aryl substituent may be C_6-20Aryl substituents, wherein R is⁷Is C with or without substituents_6-20And (4) an aryl group.

In particular, the indacenyl ligand in the metallocene compound represented by chemical formula 1 may provide a very excellent effect for the active moiety in combination with a cyclopentadienyl ligand rather than an indenyl ligand. This is because, in the steric effect of the cyclopentadienyl structure, a flat structure in which the indacenyl ligand faces the cyclopentadienyl ligand can be ensured, not the case in which the indenyl ligand is applied with the cyclopentadienyl ligand. Thus, the indacenyl structure appears to play a very beneficial role in the activation of propylene monomers by affecting the active site. This result is evidenced by the increase in tacticity of the polymerized polypropylene.

As described above, since the metallocene compound represented by chemical formula 1 is in the form that two ligands are connected through a bridge group and donate electrons to a transition metal, it may have high structural stability and high polymerization activity even if supported on a carrier.

In chemical formula 1, M may preferably be zirconium (Cr) or hafnium (Hf).

Further, in chemical formula 1, R¹And R²May be C_1-8Straight or branched alkyl, or C_2-12Straight or branched alkoxyalkyl. Specifically, it may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl or tert-butoxyhexyl.

In chemical formula 1, R³To R⁶May be C_1-6Straight or branched alkyl, or C_1-3Straight or branched chain alkyl. Specifically, it may be a methyl group, an ethyl group, a propyl group or an isopropyl group, with a methyl group being preferred.

In addition, in chemical formula 1, R⁷May be phenyl, substituted by C_1-6Phenyl, naphthyl or substituted by C, of straight-chain or branched alkyl groups_1-6Naphthyl of straight or branched alkyl. In particular, the phenyl or naphthyl group may be one or two or more thereofHydrogen is each replaced by C_1-6Straight or branched chain alkyl substituted phenyl or naphthyl. For example, R⁷The phenyl or naphthyl group of (a) may be a phenyl or naphthyl group in which one or two or more hydrogens are each substituted with a methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl group.

The substituents at each position of the aryl group can provide sufficient electrons to the aryl group by an induction effect and increase the overall size of the metallocene compound. In addition, the usable angle can be increased, and the monomer is easy to access, thereby showing better catalytic activity.

In chemical formula 1, R⁸Can be C_1-6Straight or branched alkyl, or C_1-3Straight or branched chain alkyl. In particular, it may be methyl, ethyl or propyl, preferably methyl.

In addition, the metallocene compound represented by chemical formula 1 may be represented by, for example, the following chemical formula 1-1.

[ chemical formula 1-1]

In chemical formula 1-1, M, X¹、X²、R¹、R²And R⁷As defined in chemical formula 1.

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

The metallocene compound represented by chemical formula 1 can be prepared by a known method for synthesizing an organic compound, and the following synthetic examples can be referred to for more detailed synthetic methods.

In the method of preparing the metallocene compound or the catalyst composition of the present disclosure, the equivalent weight (eq) refers to a molar equivalent weight (eq/mol).

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

In the supported metallocene catalyst according to the present disclosure, the cocatalyst co-supported on the support to activate the metallocene compound may be an organometallic compound containing a group 13 metal. However, it is not particularly limited as long as it can be used when an olefin is polymerized under a general metallocene catalyst.

Specifically, the co-catalyst may include at least one compound represented by the following chemical formula 2.

[ chemical formula 2]

-[Al(R²²)-O]_m-

In the chemical formula 2, the first and second,

R²²are identical to or different from each other and are each independently halogen, C_1-20Alkyl or C_1-20A haloalkyl group; and

m is an integer of 2 or more.

As described above, a cocatalyst can be used to further enhance the polymerization activity.

For example, the cocatalyst of formula 2 may be an alkylaluminoxane-based compound to which a repeating unit is combined in a linear, cyclic or network form. Specifically, examples of such cocatalysts include Methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane or butylaluminoxane.

In the supported metallocene catalyst according to the present disclosure, the weight ratio of the total transition metal included in the metallocene compound represented by formula 1 to the support may be 1:10 to 1: 1000. When the support and the metallocene compound are contained in the above weight ratio, an optimum shape can be exhibited. Additionally, the weight ratio of the cocatalyst to the support can be from 1:1 to 1: 100.

In the present disclosure, the supported metallocene catalyst may comprise a support containing hydroxyl groups on the surface. The carrier may preferably be dried to remove surface moisture. In addition, the carrier may have a hydroxyl group and a siloxane group (with high reactivity).

For example, the support may be silica, silica-alumina, silica-magnesia, or the like, which is dried at high temperature. In addition, the carrier may typically comprise an oxide, carbonate, sulphate or nitrate component, such as Na₂O、K₂CO₃、BaSO₄Or Mg (NO)₃)₂。

The drying temperature of the support may be preferably 200 ℃ to 800 ℃, more preferably 300 ℃ to 600 ℃, and further preferably 300 ℃ to 400 ℃. When the drying temperature of the support is less than 200 ℃, excessive moisture may exist on the surface of the support. Thus, the reaction between surface moisture and the cocatalyst can be problematic. On the other hand, when the drying temperature of the support is higher than 800 ℃, the surface area may be reduced since pores on the surface of the support may be combined. In addition, a large number of hydroxyl groups may be lost on the surface, leaving only siloxane groups, which is not preferred because of the reduced reaction sites with the cocatalyst.

The amount of hydroxyl groups on the surface of the support is preferably 0.1 to 10mmol/g, more preferably 0.5 to 5 mmol/g. The amount of hydroxyl groups on the surface of the support can be controlled by the method and conditions for preparing the support and the drying conditions (e.g., temperature, time, vacuum, or spray drying) of the support.

If the amount of hydroxyl groups is less than 0.1mmol/g, there are few reaction sites with the cocatalyst. In contrast, if the amount of the hydroxyl group exceeds 10mmol/g, it is not preferable because it may be caused by moisture other than the hydroxyl group present on the surface of the carrier particle.

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

The polymerization reaction can be conducted by contacting propylene monomer and comonomer using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

In addition, the polymerization temperature may be from about 25 ℃ to about 500 ℃, preferably from about 25 ℃ to about 200 ℃And more preferably from about 50 c to about 100 c. Further, the polymerization pressure may be about 1kgf/cm²To about 100kgf/cm²Preferably about 1kgf/cm²To about 50kgf/cm²More preferably about 10kgf/cm²To about 40kgf/cm²。

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

The supported metallocene catalyst can be injected by dissolving or diluting in the following solvents: aliphatic hydrocarbon solvents having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, or isomers thereof; or an aromatic hydrocarbon solvent such as toluene or benzene, or a hydrocarbon solvent substituted with a chlorine atom such as methylene chloride or chlorobenzene. The solvent used in the present disclosure may be preferably used by removing a small amount of water or air as a catalyst poison by pretreating a small amount of aluminum alkyl, and a cocatalyst may be further used.

As described above, the propylene-ethylene random copolymer according to the present disclosure 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 in the case where the ethylene content is increased, and ensures a low crystallization temperature and an appropriate melt index. Accordingly, the propylene-ethylene random copolymer of the present disclosure can ensure excellent processability during polymerization and injection molding. In addition, according to the propylene-ethylene random copolymer of the present disclosure, total volatile organic compound emission (TVOC) is low, and high rigidity and high transparency can be exhibited. Therefore, the propylene-ethylene random copolymer according to the present disclosure may be preferably applied to products (eco-friendly materials) for high transparency film injection.

Advantageous effects

The propylene-ethylene random copolymer according to the present disclosure maintains a high melting point even in the case where the ethylene content is increased, and ensures a low crystallization temperature and a proper melt index. Accordingly, the propylene-ethylene random copolymer of the present disclosure can ensure excellent processability during polymerization and injection molding. In addition, according to the propylene-ethylene random copolymer of the present disclosure, total volatile organic compound emission (TVOC) is low, and high rigidity and high transparency can be exhibited. Therefore, the propylene-ethylene random copolymer according to the present disclosure is advantageously used to manufacture a high transparent injection product used as an eco-friendly material.

Detailed Description

Hereinafter, the action and effect of the present invention will be described in more detail with reference to specific exemplary embodiments. However, these exemplary embodiments are provided only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Examples

< preparation of metallocene Compound >

Synthesis example 1

Preparation of ligand Compound (2-methyl-4- (3',5' -di-tert-butylphenyl) indacenyl) dimethyl (2,3,4, 5-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 eq.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (silane, 1.05 eq.) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4- (3',5' -di-t-butylphenyl) indacene (1 equivalent) was dissolved in a mixed solution of toluene/tetrahydrofuran (toluene/tetrahydrofuran, 3/2 volume ratio, 0.5M), and n-BuLi (1.05 equivalent) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of the transition Metal Compound Dimethylsilanediyl (2-methyl-4- (3',5' -di-t-butylphenyl) indacenyl) (2,3,4, 5-tetramethylcyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (toluene/diethyl ether, 2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 ℃ followed by stirring at room temperature for 5 hours. By mixing ZrCl in a separate flask₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

For the transition metal compound prepared above, a Bruker AVANCE III HD 500MHz NMR/PABBO (1H/19F/broad band) probe was used: 1H, solvent: CDCl₃NMR data was measured.

¹H-NMR(500MHz,CDCl₃)：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' -di-tert-butylphenyl) indacenyl) dimethyl (2,3,4, 5-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 eq.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (silane, 1.05 eq.) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4- (3',5' -di-t-butylphenyl) indacene (1 equivalent) was dissolved in a mixed solution of toluene/tetrahydrofuran (toluene/THF, 3/2 vol., 0.5M), and n-BuLi (1.05 equivalent) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of the transition Metal Compound Dimethylsilanediyl (2-methyl-4- (3',5' -di-t-butylphenyl) indacenyl) (2,3,4, 5-tetramethylcyclopentadienyl) hafnium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing HfCl in a separate flask₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

¹H-NMR(500MHz,CDCl₃)：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' -tert-butylphenyl) indacenyl) dimethyl (2,3,4, 5-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 eq.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq.) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4- (4' -tetrabutylphenyl) indacene (1 equivalent) was dissolved in a mixed solution of toluene/THF (3/2 vol, 0.5M), and n-BuLi (1.05 equivalent) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of the transition Metal Compound Dimethylsilanediyl (2-methyl-4- (4' -tert-butylphenyl) indacenyl) (2,3,4, 5-tetramethylcyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing ZrCl in a separate flask₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

¹H-NMR(500MHz,CDCl₃)：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-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 equiv.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq.) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, (2-methyl-4-phenyl) indacene (1 equivalent) was dissolved in a mixed solution of toluene/THF (3/2 vol, 0.5M) and n-BuLi (1.05 equivalent) was slowly added dropwise thereto at-25 ℃, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of transition metal compound dimethylsilanediyl (2-methyl-4-phenylindacenyl) (2,3,4, 5-tetramethylcyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing ZrCl in a separate flask₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, removing the residue through a filterLiCl, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

¹H-NMR(500MHz,CDCl₃)：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 the ligand Compound (2-methyl-4- (2' -naphthylene) indacenyl) dimethyl (2,3,4, 5-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 equiv.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq.) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4- (2' -naphthylene) indacene (1 equivalent) was dissolved in a mixed solution of toluene/THF (3/2 vol, 0.5M), and n-BuLi (1.05 equivalent) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of the transition Metal Compound Dimethylsilanediyl (2-methyl-4- (2' -naphthylene) indacenyl) (2,3,4, 5-tetramethylcyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By burning in a separate furnaceMixing ZrCl in bottle₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

¹H-NMR(500MHz,CDCl₃)：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' -di-tert-butylphenyl) indacenyl) diethyl (2,3,4, 5-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 equiv.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichlorodiethylsilane (1.05 eq.) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4- (3',5' -di-t-butylphenyl) indacene (1 eq) was dissolved in a mixed solution of toluene/THF (3/2 vol., 0.5M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of transition Metal Compound Diethylsilanediyl (2-methyl-4- (3',5' -di-t-butylphenyl) indacenyl) (2,3,4, 5-tetramethylcyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing ZrCl in a separate flask₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

¹H-NMR(500MHz,CDCl₃)：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 the ligand Compound (2-methyl-4- (3',5' -di (tert-butyl) phenyl) indacenyl) dihexyl (2,3,4, 5-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 equiv.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichlorodihexylsilane (1.05 eq) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4- (3',5' -di-t-butylphenyl) indacene (1 eq) was dissolved in a mixed solution of toluene/THF (3/2 vol., 0.5M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of the transition Metal Compound Dihexylsilanediyl (2-methyl-4- (3',5' -di-t-butylphenyl) indacenyl) (2,3,4, 5-tetramethylcyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing ZrCl in a separate flask₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

¹H-NMR(500MHz,CDCl₃)：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' -di-tert-butylphenyl) indacenyl) methylphenyl (2,3,4, 5-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 equiv.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichloromethylphenylsilane (1.05 eq) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4- (3',5' -di-t-butylphenyl) indacene (1 eq) was dissolved in a mixed solution of toluene/THF (3/2 vol., 0.5M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of the transition Metal Compound Methylphenylsilanediyl (2-methyl-4- (3',5' -di-t-butylphenyl) indacenyl) (2,3,4, 5-tetramethylcyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing ZrCl in a separate flask₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

¹H-NMR(500MHz,CDCl₃)：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 the ligand Compound (2-methyl-4- (3',5' -di-tert-butylphenyl) indacenyl) methylhexyl (2,3,4, 5-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 equiv.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichloromethylhexylsilane (1.05 eq.) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4- (3',5' -di-t-butylphenyl) indacene (1 eq) was dissolved in a mixed solution of toluene/THF (3/2 vol., 0.5M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of transition Metal Compound Methylhexylsilanediyl (2-methyl-4- (3',5' -di-t-butylphenyl) indacenyl) (2,3,4, 5-tetramethylcyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing ZrCl in a separate flask₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

¹H-NMR(500MHz,CDCl₃)：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-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 equiv.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq.) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4- (2 ',5' -dimethylphenyl) indacene (1 equivalent) was dissolved in a mixed solution of toluene/THF (3/2 vol, 0.5M) and n-BuLi (1.05 equivalent) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of the transition Metal Compound Dimethylsilanediyl (2-methyl-4- (2 ',5' -dimethylphenyl) indacenyl) (2,3,4, 5-tetramethylcyclopentadienyl) hafnium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing HfCl in a separate flask₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

¹H-NMR(500MHz,CDCl₃)：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 the ligand Compound (2-methyl-4- (3',5' -di-tert-butylphenyl) indacenyl) 6- (tert-butoxy) -hexylmethyl (2,3,4, 5-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 equiv.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichloro-6- (tert-butoxy) -hexylmethylsilane (1.05 eq) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4- (3',5' -di-t-butylphenyl) indacene (1 eq) was dissolved in a mixed solution of toluene/THF (3/2 vol., 0.5M), and n-BuLi (1.05 eq) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of the transition Metal Compound 6- (tert-butoxy) -hexylmethyl-silanediyl (2-methyl-4- (3',5' -di-tert-butylphenyl) indacenyl) (2,3,4, 5-tetramethylcyclopentadienyl) hafnium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing HfCl in a separate flask₄(1 eq) and toluene (0.17M) toA slurry was prepared and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

¹H-NMR(500MHz,CDCl₃)：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 the ligand Compound (2-methyl-4- (4' - (tert-butyl) -phenyl) inden-1-yl) dimethyl (2,3,4, 5-tetramethylcyclopentadienyl) silane

2,3,4, 5-Tetramethylcyclopentadiene (TMCP) was dissolved in Tetrahydrofuran (THF), and n-butyllithium (n-BuLi, 1.05 equiv.) was slowly added dropwise thereto at-25 deg.C, followed by stirring at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq.) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4- (4' - (tert-butyl) -phenyl) indene (1 eq) was dissolved in a mixed solution of toluene/THF (3/2 vol, 0.5M) and n-BuLi (1.05 eq) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of the transition Metal Compound Dimethylsilanediyl (2-methyl-4- (4' - (tert-butyl) -phenyl) inden-1-yl) (2,3,4, 5-tetramethylcyclopentadienyl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing ZrCl in a separate flask₄(1 eq.) and toluene (1.2M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

Comparative Synthesis example 2

Preparation of the ligand Compound bis (2-methyl-4- (4' - (tert-butyl) -phenyl) inden-1-yl) silane

2-methyl-4- (4' - (tert-butyl) -phenyl) indene (1 equivalent) was dissolved in a mixed solution of toluene/THF (10/1 vol., 0.3M), and n-butyllithium (n-BuLi, 2.1 equivalents) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then dichlorodimethylsilane (0.53 eq) was added thereto at-10 ℃ and stirred at room temperature overnight. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of the transition Metal Compound Dimethylsilanediylbis (2-methyl-4- (4' - (tert-butyl) -phenyl) inden-1-yl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (10/1 vol., 0.1M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing ZrCl in a separate flask₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

Comparative Synthesis example 3

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

2-isopropyl-4- (4' -tert-butylphenyl) -1-indene (1 equivalent) was dissolved in tetrahydrofuran/hexane (THF/hexane, 1/10 vol.0.3M), and n-butyllithium (n-BuLi, 1.05 equivalent) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq.) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 4- (4' -tert-butylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-7-indacene (1 equivalent) was dissolved in a mixed solution of toluene/tetrahydrofuran (toluene/THF, 3/2 volume ratio, 0.5M), and n-BuLi (1.05 equivalent) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of the transition Metal Compound Dimethylsilanediyl (4- (4 '-tert-butylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacen-7-yl) (2-isopropyl-4- (4' -tert-butylphenyl) -inden-1-yl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing ZrCl in a separate flask₄(1 eq.) and toluene (1.2M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

Comparative Synthesis example 4

Preparation of the ligand Compound (2-methyl-4- (4 '-tert-butylphenyl) -tetrahydrocyclopenta [ b ] naphthalene) dimethyl (2-isopropyl-4- (4' -tert-butylphenyl) indenyl) silane

Methacryloyl chloride (37.5mL, 375mmol) was added to CH at-70 deg.C₂Cl₂(600mL) well stirred AlCl₃(100g, 750 mmol). After stirring for 20 min, tetrahydronaphthalene (49.5g,375mmol) was added. The temperature of the reaction mixture was raised to room temperature and stirred for a further 16 hours. After that, the reaction mixture was poured into ice water-HCl (1L/150 mL). Then, the organic layer was separated, and the aqueous layer was treated with CH₂Cl₂(2100 mL). The combined organic phases were washed sequentially with water, aqueous NaHCO₃Washing with MgSO 2₄Dried and evaporated. After vacuum distillation (130 ℃ to 140 ℃/0.5 torr), a ketone mixture was obtained. The desired isomer then remains liquid after 5 days of storage and can be isolated by decantation. Yield: 30g (40%).

Reacting the CH prepared above at-20 deg.C₂Cl₂2-methyl-2, 3,5,6,7, 8-hexahydro-1H-cyclopenta [ b ] in (50mL)]Naphthalen-1-one (30g, 150mmol) with CH₂Cl₂AlCl in (250mL)₃(40g, 300mmol) of the suspensionMixing the floating liquid. After stirring for 20 minutes, Br was added to the reaction₂(7.7ml, 150 mmol). The temperature of the reaction mixture was raised to room temperature and stirred for a further 16 hours. After that, the reaction mixture was poured into ice water-HCl (500mL/70 mL). Then, the organic layer was separated, and the aqueous layer was treated with CH₂Cl₂(50mL, twice) extracted. The combined organic phases are successively treated with water and aqueous KHCO₃Washing with MgSO 2₄Dried and evaporated. The residue was distilled under vacuum (175 ℃ C. to 180 ℃ C./0.5 torr) to give 31g (74%) of the reaction product, i.e., 2-methyl-2, 3,5,6,7, 8-hexahydro-1H-cyclopenta [ b ] e]1-naphthalen-ones.

Make Pd (OAc)₂(0.74g, 3 mol%) and PPh₃(1.73g, 6 mol%) with 2-methyl-2, 3,5,6,7, 8-hexahydro-1H-cyclopenta [ b ] e]Naphthalen-1-one (31g, 110mmol), tert-butylphenyl boronic acid (26.7g, 150mmol) and Na₂CO₃(31.8g, 300mmol) in well stirred dimethoxyethane (380mL)/H₂Combined in O (130 mL). The resulting mixture was refluxed for 6 hours with stirring, cooled, poured into water (700mL) and extracted with benzene (4 times 100mL each). The resulting solution was filtered and evaporated. Reacting the reaction product, 4- (4-tert-butylphenyl) -2-methyl-2, 3,5,6,7, 8-hexahydro-1H-cyclopenta [ b]Naphthalene-1-one was subjected to column chromatography (silica gel 60, hexane/CH)₂Cl₂1: 1). The yield was 18.3g (50%).

Subjecting LiAIH to a reaction at-20 deg.C₄(0.95g, 25mmol) was added to the above product 4- (4-tert-butylphenyl) -2-methyl-2, 3,5,6,7, 8-hexahydro-1H-cyclopenta [ b ] b]Naphthalen-1-one (16.6g, 50mmol) was dissolved in diethyl ether (Et)₂O, 150 mL). The temperature of the reaction mixture was raised to room temperature and further stirred for 1 hour. Thereafter, 5% HCl (100mL) was added to the reaction and the resulting mixture was treated with Et₂O (3X 50mL) extraction. The combined organic phases were washed successively with water and MgSO₄Dried and evaporated. Benzene (300mL) and p-TSA (0.5g) were added and the resulting solution refluxed with a Dean-Stark head (controlled by TLC, benzene/EtOAc 4:1) over 4 hours. Then, the obtained solution is mixed with water or aqueous KHCO₃Washing and purifying with MgSO 2₄And (5) drying. Thereafter, the residue was passed through silica gel and evaporated to give 12.78g (81%) of the reaction product, 9- (4-tert-butylbenzene)Yl) -2-methyl-5, 6,7, 8-tetrahydro-1H-cyclopenta [ b]Naphthalene.

The above 9- (4-tert-butylphenyl) -2-methyl-5, 6,7, 8-tetrahydro-1H-cyclopenta [ b ]]Naphthalene (2.97g, 9.38mmol) in Et₂The solution in O (50mL) was cooled to-60 ℃ and n-BuLi (1.6M in hexane, 6.04mL, 9.67mmol) was added. The resulting mixture was warmed to room temperature, stirred for 3 hours, and cooled to-60 ℃. Then, CuCN (50mg, 0.55mmol) was added. After stirring for 15 min, chloro- (4- (4-tert-butylphenyl) -2-isopropyl-1H-inden-1-yl) -dimethylsilane (9.67mmol) in Et is added₂Solution in O (24 mL). The resulting mixture was warmed to room temperature and stirred for 16 hours. Then, water (5mL) and hexane (200mL) were added. Thereafter, the organic phase is separated off over MgSO₄Dried, passed through silica gel and evaporated. Reaction product [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 was dried in vacuo and used without purification.

Preparation of the transition Metal Compound Dimethylsilanediyl (2-methyl-4- (4 '-tert-butylphenyl) -tetrahydrocyclopenta [ b ] naphthalene) (2-isopropyl-4- (4' -tert-butylphenyl) indenyl) zirconium dichloride

The ligand compound [4- (4-tert-butylphenyl) -2-isopropyl-1H-inden-1-yl ] prepared above is mixed][4- (4-tert-butylphenyl) -2-methyl-5, 6,7, 8-tetrahydro-1H-cyclopenta [ b ]]Naphthalen-1-yl]Dimethylsilane (5.82g, 8.78mmol) was dissolved in Et₂O (60mL), cooled to-40 ℃ and n-BuLi (1.6M in hexane, 11.52mL, 18.44mmol) was added. The reaction mixture was warmed to room temperature, stirred for 3 hours and evaporated. The residue was suspended in pentane (100mL), cooled to-60 ℃ and ZrCl was added₄(2.15g, 9.22 mmol). After 5 min Et was added₂O (1 mL). The resulting mixture was warmed to room temperature, stirred for another 16 hours, and filtered. The resulting yellow-orange powder was dried, dimethoxyethane (100mKL) and LiCl (0.3g) were added, and the mixture was refluxed for 6 hours with stirring. Followed by dimethoxyethane and CH₂Cl₂/Et₂And O recrystallizing to obtain the product. The yield of the resulting rock-like product was 0.88g (24.4%).

Comparative Synthesis example 5

Preparation of the ligand Compound [ (6-tert-butoxyhexyl) (methyl) -bis [ 2-methyl-4-phenyl) -inden-1-yl ] silane

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

To 77mL of a 2-methyl-4-phenylindene toluene/THF-10/1 solution (34.9mmol) at 0 ℃ was slowly added dropwise a solution of 15.4mL of n-butyllithium (2.5M, hexane solvent) and stirred at 80 ℃ for 1 hour. Thereafter, the reaction mixture was stirred at room temperature for one day. Then, 5g of (6-t-butoxyhexyl) dichloromethylsilane prepared above was slowly added dropwise to the reaction mixture at-78 ℃ with stirring for about 10 minutes, and then stirred at 80 ℃ for 1 hour. Then, water was added to separate an organic layer, which was purified through a silica column and dried under vacuum to obtain a viscous yellow oil in a yield of 78% (racemate: meso ═ 1: 1).

¹H NMR(500MHz,CDCl₃)：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 the transition Metal Compound [ (6-tert-Butoxyhexylmethylsilanediyl) -bis [ 2-methyl-4- (4' -tert-butylphenyl) ] zirconium dichloride

The ligand compound (6-tert-butoxyhexyl) (methyl) bis (2-methyl-4-phenyl) indenylsilaneethyl ether/hexane-1/1 solution (3.37mmol) prepared above was slowly added dropwise at-78 ℃ in 50mL of n-butyl 3.0mL of lithium solution (2.5M in hexane), stirred at room temperature for about 2 hours, and then dried in vacuo. The salt was washed with hexane and,filtered and dried under vacuum to obtain a yellow solid. The ligand salt synthesized in the glove box and bis (N, N' -diphenyl-1, 3-propanediamido) zirconium dichloride bis (tetrahydrofuran) [ Zr (C) were weighed in a shrink flask₅H₆NCH₂CH₂NC₅H₆)Cl₂(C₄H₈O)₂]And diethyl ether was slowly added dropwise at-78 ℃ followed by stirring at room temperature for one day. Thereafter, the red reaction solution was separated by filtration, and 4 equivalents of ethereal HCl (1M) was slowly added dropwise at-78 ℃ followed by stirring at room temperature for 3 hours. After filtration and vacuum drying, the ansa metallocene compound was obtained as an orange solid component in a yield of 85% (racemate: meso ═ 1: 1).

¹H NMR(500MHz,C₆D₆,7.24ppm)：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 the ligand Compound (2-methyl-4-phenyl) indacen-1-yl) dimethyl (cyclopentadienyl) silane

Dicyclopentadiene was condensed by cleavage at 150 ℃ to extract cyclopentadiene, and cyclopentadiene (1 equivalent) was dissolved in THF (0.3M). Then, n-BuLi (1.05 eq.) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq.) was added thereto at-10 ℃ and stirred at room temperature overnight. In another reactor, 2-methyl-4-phenylindacene (1 equivalent) was dissolved in a mixed solution of toluene/THF (3/2 vol: 0.5M), and n-BuLi (1.05 equivalent) was slowly added dropwise thereto at-25 ℃ followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and then the first reaction product, a single-crystal silicon solution, was added thereto. After that, it was stirred at room temperature overnight, treated with water and dried to obtain a ligand.

Preparation of transition Metal Compound dimethyl-silanediyl (cyclopentadienyl) (2-methyl-4-phenyl) indacenyl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene/diethyl ether (2/1 vol., 0.53M), and n-BuLi (2.05 eq.) was added at-25 deg.C, followed by stirring at room temperature for 5 hours. By mixing ZrCl in a separate flask₄(1 eq.) and toluene (0.17M) were made into a slurry and added to the ligand solution, followed by stirring at room temperature overnight. Upon completion of the reaction, the solvent was dried in vacuo, and dichloromethane was added thereto. Then, LiCl was removed through a filter, and the filtrate was dried in vacuo, and methylene chloride/hexane was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to obtain the metallocene compound described above.

¹H-NMR(500MHz,CDCl₃)：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

100g of silica support (silica gel, SYLOPOL 952X, calcined at 250 ℃) were placed in a 2L reactor under an argon (Ar) atmosphere and 766mL of Methylaluminoxane (MAO) were slowly added at room temperature, followed by stirring at 90 ℃ for 15 hours. After completion of the reaction, the mixture was allowed to cool to room temperature and left to stand for 15 minutes, and the solvent was poured out using a cannula. 400mL of toluene was added, stirred for 1 minute, allowed to stand for 15 minutes, and the solvent was poured out using a cannula.

Mu. mol of the metallocene compound prepared in Synthesis example 1 was dissolved in 400mL of toluene and transferred to the reactor using a cannula. After stirring at 50 ℃ for 5 hours, the mixture was allowed to cool to room temperature and left to stand for 15 minutes, and the solvent was poured out using a cannula. 400mL of toluene was added, stirred for 1 minute, and left to stand for 15 minutes, and the solvent was poured out using a cannula. This process was repeated 2 times. In the same manner, 400mL of hexane was added thereto, stirred for 1 minute, and then left to stand for 15 minutes, and the solvent was decanted off using a cannula. Thereafter, the antistatic agent (Atmer 163, 3g) was dissolved in 400mL of hexane, and then transferred to the reactor using a cannula. Thereafter, the solvent was removed by stirring at room temperature for 20 minutes, and transferred through a glass filter.

Dried under vacuum at room temperature for 5 hours, and then dried under vacuum at 45 ℃ for 4 hours to obtain a supported catalyst.

Preparation examples 2 to 12

A silica-supported metallocene catalyst was prepared in the same manner as in preparation example 1, except that each of the metallocene compounds of Synthesis examples 2 to 12 was used in place of the metallocene compound of Synthesis example 1, respectively.

Comparative preparation examples 1 to 6

A silica-supported metallocene catalyst was prepared in the same manner as in preparation example 1, except that each of the metallocene compounds of comparative synthesis examples 1 to 6 was used instead of the metallocene compound of synthesis example 1, respectively.

< random copolymerization of propylene and ethylene >

Example 1

Bulk slurry polymerization of propylene and ethylene was carried out using two continuous loop reactors in the presence of the silica-supported metallocene catalyst prepared in preparation example 1.

At this time, for bulk slurry polymerization, the supported catalyst prepared according to preparation example 1 was used in the form of a slurry catalyst mixed with oil and grease at 16 wt%. The catalyst mixture prepared above was introduced into a prepolymerization reactor together with about 20kg/hr of propylene, and continuously introduced into a loop reactor after a residence time of 8 minutes or more. At this point, hydrogen was introduced together with propylene flowing into the loop reactor, the reactor temperature was maintained at about 70 ℃ and the reactor pressure was maintained at about 35kg/cm²The pressure of (a). At this time, hydrogen was fed in an amount of about 150ppm based on the amount of propylene (C3) continuously fed. Alternatively, ethylene (C2) was introduced directly into the ring reactorThe reactor was such that it was 3.5% by weight based on the continuously fed amount of propylene (C3), and a bulk slurry polymerization process was carried out.

Examples 2 to 12

Bulk slurry polymerization of propylene and ethylene was carried out in the same manner as in example 1 except that each of the silica-supported metallocene catalysts of preparation examples 2 to 12 was used instead of the silica-supported metallocene catalyst of preparation example 1, respectively.

Comparative example 1

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 2.0% by weight based on the input amount 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% by weight based on the input amount of propylene (C3).

Comparative example 3

Bulk slurry polymerization of propylene and ethylene was carried out in the same manner as in example 1 except that a Ziegler-Natta (Z/N) catalyst (manufacturer: Lyondelbasell, product name: ZN127VS) was used in place of the metallocene catalyst, and the input amount of ethylene (C2) was changed to 3.0% by weight based on the input amount of propylene (C3).

Comparative example 4

Bulk slurry polymerization of propylene and ethylene was carried out in the same manner as in example 1, except that the silica-supported metallocene catalyst prepared in comparative preparation example 1 was used as the metallocene catalyst, and the input amount of ethylene (C2) was changed to 2.0 wt% based on the input amount of propylene (C3).

Comparative example 5

Bulk slurry polymerization of propylene and ethylene was carried out in the same manner as in comparative example 4, except that the input amount of ethylene (C2) was changed to 2.5% by weight based on the input amount of propylene (C3).

Comparative example 6

Bulk slurry polymerization of propylene and ethylene was carried out in the same manner as in comparative example 4, except that the input amount of ethylene (C2) was changed to 3.5% by weight based on the input amount of propylene (C3), but fouling (fouling) occurred during the polymerization.

Comparative example 7

Bulk slurry polymerization of propylene and ethylene was carried out in the same manner as in example 1, except that the silica-supported metallocene catalyst prepared in comparative preparation example 2 was used as the metallocene catalyst, and the input amount of ethylene (C2) was changed to 3.0 wt% based on the input amount of propylene (C3).

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% by weight based on the input amount 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 input amount of ethylene (C2) was changed to 6.0% by weight based on the input amount of propylene (C3), but fouling (fouling) occurred during the polymerization.

Comparative example 10

Bulk slurry polymerization of propylene and ethylene was carried out in the same manner as in example 1, except that the silica-supported metallocene catalyst prepared in comparative preparation example 3 was used as the metallocene catalyst, and the input amount of ethylene (C2) was changed to 6.0 wt% based on the input amount of propylene (C3).

Comparative example 11

Bulk slurry polymerization of propylene and ethylene was carried out in the same manner as in example 1, except that the silica-supported metallocene catalyst prepared in comparative preparation example 4 was used as the metallocene catalyst, and the input amount of ethylene (C2) was changed to 5.5% by weight based on the input amount of propylene (C3).

Comparative example 12

Bulk slurry polymerization of propylene and ethylene was carried out in the same manner as in example 1, except that the silica-supported metallocene catalyst prepared in comparative preparation example 5 was used as the metallocene catalyst, and the input amount of ethylene (C2) was changed to 4.5% by weight based on the input amount of propylene (C3).

Comparative example 13

Bulk slurry polymerization of propylene and ethylene was carried out in the same manner as in example 1, except that the silica-supported metallocene catalyst prepared in comparative preparation example 6 was used as the metallocene catalyst, and the input amount of ethylene (C2) was changed to 2.0 wt% based on the input amount of propylene (C3).

< Experimental example >

Evaluation of physical Properties of propylene-ethylene random copolymer

Physical properties of the propylene-ethylene random copolymers prepared in examples and comparative examples were evaluated in the following manner.

(1) Comonomer content (C2, wt. -%)

Comonomer content was determined according to the american society for testing and materials ASTM D5576 as follows: a film or film-like sample of the propylene random copolymer was fixed on a magnetic holder of an FT-IR apparatus, and the IR absorption spectrum was measured at 4800cm^-1To 3500cm^-1The peak height in which the thickness of the sample is reflected, and 710cm^-1To 760cm^-1Indicates the peak area of the ethylene component, and then the measurement value is substituted into the calibration equation (710 cm of the standard sample^-1To 760cm^-1Area of the peak in (1) divided by 4800cm^-1To 3500cm^-1Plotted against the value obtained for peak height in (1).

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

The melting point (Tm) and crystallization temperature (Tc) of the propylene random copolymer were measured using a differential scanning calorimeter (DSC, equipment name: DSC 2920, manufacturer: TA instrument).

In detail, the polypropylene polymer is heated to 200 ℃ by increasing the temperature, then held at this temperature for 5 minutes, after which the temperature is reduced to 30 ℃. Then, the temperature was increased again, and the temperature corresponding to the peak in the DSC (differential scanning calorimeter, manufactured by TA) curve was determined as the melting point (Tm). Thereafter, when the temperature was again decreased to 30 ℃, the top of the curve was taken as the crystallization temperature (Tc). In this regard, the temperature is increased and decreased at a rate of 10 deg.C/min, respectively, and the melting point (Tm) and crystallization temperature (Tc) are the results measured at the second temperature increase and decrease sections.

(3) Melt index (melt index, MI)

The melt index was determined at 230 ℃ under a 2.16kg load according to ASTM D1238 method of the American society for testing and materials and is expressed as the weight (g) of polymer melted for 10 minutes.

(4) Haze (%)

The light refractivity (%) was measured when a 1T (1mm) propylene-ethylene random copolymer specimen was irradiated with light according to ASTM D1003 of the American society for testing and materials, American society for testing and materials. The transparency of the haze measurement specimen was Td (refracted light)/Tt (transmitted light). times.100 (%)

(5) Xylene solubles (X.S, wt%)

Each sample of the propylene-ethylene random copolymer was mixed with xylene and dissolved at 135 ℃ for 1 hour, and then cooled for 30 minutes to perform pretreatment. Xylene was flowed in an OminiSec (FIPA from Viscotek) apparatus at a flow rate of 1mL/min for 4 hours and stabilized for RI (refractive index), DP (bridge intermediate pressure), IP (bridge top to bottom inlet pressure). Thereafter, the concentration and the injection amount of the pretreated sample were recorded and measured, and then the peak area was calculated.

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

The total volatile organic compound emission (TVOC, ppm) contained in the propylene-ethylene random copolymer was measured according to the VDA 277 method using a headspace-GC (gas chromatography) apparatus.

Table 1 shows the evaluation results of the physical properties of the propylene-ethylene random copolymer measured by the above-mentioned methods.

[ TABLE 1]

As shown in table 1 above, the propylene-ethylene random copolymers of examples 1 to 12 according to the embodiments of the present disclosure ensure a high melting point (Tm) of 125.2 ℃ to 126.2 ℃ to increase the ethylene (C2) content in the copolymer while maintaining improved process stability and other injectability properties. In addition, it was confirmed that the increased content of ethylene (C2) exhibited the characteristic of decreasing crystallinity, thereby improving transparency. In addition, in the case of examples 1 to 12, it can be seen that TVOC is very low, and thus eco-friendliness can be ensured using a highly transparent propylene-ethylene random copolymer for food containers and the like.

In contrast, even in comparative examples 1 and 2 using the catalyst precursor of preparation example 1 identical to example 1, as the input amount of ethylene (C2) during polymerization was decreased, the ethylene (C2) content of the copolymer was decreased, and haze of 8.3% and 7.8% was obtained, and it can be seen that transparency was decreased.

In addition, comparative example 3 using a Ziegler-Natta (Z/N) catalyst showed that, although the content of ethylene (C2) was high, blocky heterogeneous copolymerization of ethylene (C2) occurred in the polymer structure of ethylene (C2), resulting in a very high crystallization temperature (Tc) of 111 ℃, a very high TVOC of 310ppm, and a very high random xylene solubles content (XS) of 4.5 wt%.

On the other hand, in comparative examples 4 to 6, catalyst compositions containing no indacene ligand but containing a metallocene compound of a well-known ligand containing a cyclopentadienyl group were used, provided that the Tm range in which fouling does not occur was maintained. Increasing the ethylene (C2) content is limited and therefore a certain degree of transparency cannot be achieved. In particular, in comparative example 6, fouling occurred during the polymerization, and the physical properties of the copolymer could not be evaluated.

Therefore, in comparative examples 7 to 9, in which the catalyst composition of comparative preparation example 2 (comprising a metallocene compound having a bridged indenyl ligand instead of a cyclopentadienyl (Cp) ligand bridged with an indacene ligand) was used, basically, as the Tm of the homopolypropylene itself was low, when the ethylene (C2) content was increased, fouling occurred, and it was impossible to maintain a certain level of the ethylene (C2) content. In addition, ethylene (C2) is less reactive and therefore the input of ethylene (C2) must be very high to ensure an equivalent level of ethylene content in the copolymer. In particular, in the case of comparative example 9, fouling occurred during the polymerization, and the physical properties of the copolymer could not be evaluated.

In addition, in comparative examples 10 to 12 using the catalyst composition comprising the metallocene compound having a bis-indenyl (or indacenyl) group, the ethylene conversion (C2 conversion) was very low, and therefore the input amount of ethylene (C2) at the time of copolymerization had to be high. It is possible to increase the content of ethylene (C2) in the main body to a certain level or more, and there is a limit to increase the content of ethylene (C2), and thus a certain degree of transparency cannot be achieved.

On the other hand, in the case of comparative example 13, since the structure does not have racemate selectivity (the polypropylene is made directional), random polypropylene is produced, and therefore, the physical properties of the copolymer cannot be evaluated.