KR102693458B1 - Polyethylene and its chlorinated polyethylene - Google Patents

Abstract

Polyethylene according to the present invention implements a molecular structure with increased polymer content, minimizes changes in crystal structure during reaction with chlorine, and produces chlorinated polyethylene with excellent chlorination productivity and thermal stability.

Description

Polyethylene and its chlorinated polyethylene {POLYETHYLENE AND ITS CHLORINATED POLYETHYLENE}

The present invention relates to polyethylene and chlorinated polyethylene thereof, which can produce chlorinated polyethylene with excellent chlorination productivity and thermal stability by increasing the high molecular weight content in the molecular structure.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed to suit their respective characteristics. The Ziegler-Natta catalyst has been widely applied to existing commercial processes since its invention in the 1950s. However, because it is a multi-site catalyst with multiple active sites, it is characterized by a wide molecular weight distribution of the polymer and comonomer. There is a problem that there is a limit to securing the desired physical properties because the composition distribution is not uniform.

Meanwhile, a metallocene catalyst is composed of a combination of a main catalyst mainly composed of transition metal compounds and a cocatalyst which is an organometallic compound mainly composed of aluminum. Such a catalyst is a homogeneous complex catalyst and is a single-site catalyst. ), and a polymer with a narrow molecular weight distribution due to the single active site characteristics and a uniform composition distribution of the comonomer is obtained, and the stereoregularity, copolymerization characteristics, and molecular weight of the polymer are obtained by modifying the ligand structure of the catalyst and changing the polymerization conditions. It has properties that can change crystallinity, etc.

U.S. Patent No. 5,914,289 describes a method of controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used and the manufacturing time are large when producing the supported catalyst. , there was the inconvenience of having to support each metallocene catalyst used on a carrier.

Korean Patent Application No. 2003-12308 discloses a method of controlling molecular weight distribution by supporting a dinuclear metallocene catalyst and a mononuclear metallocene catalyst together with an activator on a carrier and polymerizing them while changing the combination of catalysts in the reactor; there is. However, this method has limitations in realizing the characteristics of each catalyst simultaneously, and also has the disadvantage of causing fouling in the reactor because the metallocene catalyst portion is released from the carrier component of the completed catalyst.

Accordingly, in order to solve the above-mentioned shortcomings, there continues to be a need for a method of producing an olefin-based polymer with desired physical properties by simply preparing a hybrid supported metallocene catalyst with excellent activity.

Meanwhile, chlorinated polyethylene, manufactured by reacting polyethylene and chlorine, is known to have improved physical and mechanical properties compared to polyethylene, and can withstand even harsh external environments, so it is used as packing materials such as various containers, fibers, pipes, etc. Used as a material.

Chlorinated polyethylene is generally manufactured by making polyethylene in a suspension state and then reacting with chlorine, or by placing polyethylene in an aqueous HCl solution and reacting with chlorine to replace the hydrogen in polyethylene with chlorine.

In order to fully express the properties of chlorinated polyethylene, chlorine must be uniformly substituted in polyethylene, which is affected by the properties of polyethylene that reacts with chlorine. In particular, chlorinated polyethylene such as CPE (Chlorinated Polyethylene) is widely used as an impact modifier for pipes and window profiles through compounding with PVC. It is generally manufactured by reacting polyethylene with chlorine in a suspension state. , it can be produced by reacting polyethylene with chlorine in an HCl aqueous solution. In this CPE manufacturing process, the chlorination reaction that introduces chlorine is carried out at a high temperature, so it becomes a critical step that determines the time of post-processes such as deoxidation and drying processes depending on the level of thermal strain of the polyethylene powder. However, if thermal deformation occurs during this process and the pores of the polyethylene powder become narrowed or blocked, the time required for the deoxidation process to remove hydrochloric acid generated as a by-product in the chlorination process and the drying process to remove moisture increases.

Accordingly, there is a continued need for the development of technology that can produce polyethylene with a molecular structure with an increased high molecular weight content in order to prevent productivity reduction problems in the chlorination process for producing chlorinated polyethylene.

The present invention seeks to provide polyethylene and chlorinated polyethylene thereof, which can produce chlorinated polyethylene with excellent chlorination productivity and thermal stability by implementing a molecular structure with increased polymer content.

Additionally, the present invention seeks to provide a method for producing the polyethylene.

According to one embodiment of the invention, polyethylene is provided, having a melt index (MI ₅ ) of 0.1 to 1.0 g/10 min as measured at 190° C. under a load of 5 kg by the method of ASTM D 1238, a molecular weight distribution (Mw/Mn) of 2 to 4.8, and a thermal stability index (TSI) of Equation 1 below of greater than 0 and less than or equal to 50.

[Equation 1]

TSI = (k1×M1) + (k2×M2) + (k3×M3) +k4

In equation 1,

M1 is the ratio (%) of the integral value in the area where Log Mw is 5.0 or more to less than 5.5 to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

M2 is the ratio (%) of the integral value in the area where Log Mw is 5.5 or more to less than 6.0 to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

M3 is the ratio (%) of the integral value of the area where Log Mw is 6.0 or more to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

k1 is 2.15 to 2.65, k2 is -6.95 to -5.65, k3 is -17.4 to -14.2, and k4 is 110.5 to 135.5.

Here, M1, M2, and M3 are values obtained through a molecular weight measurement method using a gel permeation chromatography (GPC) device, and k1, k2, k3, and k4 are values obtained by a linear regression analysis method.

Additionally, the present invention provides a method for producing the polyethylene.

Additionally, the present invention provides chlorinated polyethylene produced by reacting the polyethylene with chlorine.

Additionally, the present invention provides a PVC composition comprising the chlorinated polyethylene and vinyl chloride polymer (PVC).

The polyethylene according to the present invention has a molecular structure with an increased polymer content, thereby minimizing changes in the crystal structure during reaction with chlorine, making it possible to produce chlorinated polyethylene with excellent chlorination productivity and thermal stability.

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

Additionally, the terminology used herein is only used to describe exemplary embodiments and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as “comprise,” “comprise,” or “have” are intended to designate the presence of implemented features, numbers, steps, components, or a combination thereof, and are intended to indicate the presence of one or more other features or It should be understood that this does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.

Since the present invention can make various changes and take various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

Hereinafter, the present invention will be described in more detail.

According to one embodiment of the invention, polyethylene that can produce chlorinated polyethylene with excellent chlorination productivity and thermal stability by implementing a molecular structure with increased polymer content is provided.

The polyethylene has a melt index (MI ₅ ) of 0.1 g/10min to 1.0 g/10min, measured at 190°C and 5 kg load by the method of ASTM D 1238, and a molecular weight distribution (Mw/Mn) of 2 to 4.8, It is characterized in that the Thermal Stability Index (TSI) of Equation 1 below is greater than 0 and less than or equal to 50.

[Equation 1]

TSI = (k1×M1) + (k2×M2) + (k3×M3) +k4

In equation 1,

M1 is the ratio (%) of the integral value in the area where Log Mw is 5.0 or more to less than 5.5 to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

M2 is the ratio (%) of the integral value in the area where Log Mw is 5.5 or more to less than 6.0 to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

M3 is the ratio (%) of the integral value of the area where Log Mw is 6.0 or more to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

k1 is 2.15 to 2.65, k2 is -6.95 to -5.65, k3 is -17.4 to -14.2, and k4 is 110.5 to 135.5.

Here, M1, M2, and M3 are values obtained through a molecular weight measurement method using a gel permeation chromatography (GPC) device as described later, and k1, k2, k3, and k4 are values obtained by a linear regression analysis method. am.

In general, chlorinated polyethylene is manufactured by reacting polyethylene with chlorine, meaning that some of the hydrogen in polyethylene is replaced with chlorine. When hydrogen in polyethylene is replaced with chlorine, the properties of polyethylene change because the atomic volumes of hydrogen and chlorine are different. For example, chlorination productivity and thermal stability increase. In particular, the smaller and more uniform the overall size of the chlorinated polyethylene particles are, the easier it is for chlorine to penetrate into the center of the polyethylene particles, so the degree of chlorine substitution within the particles is uniform and excellent physical properties can be exhibited. To this end, the polyethylene according to the present invention has a small molecular weight distribution. , it is possible to provide chlorinated polyethylene that can have better chlorination productivity and thermal stability by increasing the polymer content in the molecular structure.

The polyethylene of the present invention can produce chlorinated polyethylene with excellent chlorination productivity and thermal stability by increasing the polymer content in the molecular structure.

Polyethylene according to the present invention may be an ethylene homopolymer that does not contain a separate copolymer.

As described above, the polyethylene has a melt index MI _{5 of 0.1 g/10min to 1.0 g/10min, or 0.1 g/10min to 0.4 g/, as measured by the method of ASTM D 1238 under the conditions of a temperature of 190°C and a load of 5 kg} . It could be 10min. This means that the melt index MI ₅ of polyethylene is low and the content of high molecular weight components is high, which causes the effect of increasing chlorination productivity and thermal stability.

Preferably, the density of the polyethylene may be 0.947 g/cm ³ to 0.954 g/cm ³ , or 0.950 g/cm ³ to 0.952 g/cm ³ . This means that the content of the crystal structure of polyethylene is high and dense, and it has the characteristic that changes in the crystal structure are difficult to occur during the chlorination process.

The polyethylene of the present invention is characterized by having a narrow molecular weight distribution along with the melt index characteristics described above.

The polyethylene according to the present invention may have a molecular weight distribution of 2 to 4.8, alternatively 3 to 4.7, or 3.5 to 4.6. This means that the molecular weight distribution of polyethylene is narrow. If the molecular weight distribution is wide, the difference in molecular weight between polyethylenes is large, so the chlorine content between chlorinated polyethylenes may vary after the chlorination reaction, making uniform distribution of chlorine difficult. In addition, when low molecular weight components are melted, they have high fluidity and can block the pores of polyethylene particles, reducing chlorination productivity. However, in the present invention, since the molecular weight distribution is as described above, the difference in molecular weight between polyethylene after the chlorination reaction is not large, so chlorine can be substituted uniformly.

As an example, the molecular weight distribution (MWD, polydispersity index) is measured by measuring the weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene using gel permeation chromatography (GPC, manufactured by Water), It can be calculated by dividing the weight average molecular weight by the number average molecular weight.

Specifically, as a gel permeation chromatography (GPC) device, a Waters PL-GPC220 instrument can be used, and a Polymer Laboratories PLgel MIX-B 300 mm long column can be used. At this time, the measurement temperature is 160 ℃, 1,2,4-trichlorobenzene can be used as a solvent, and the flow rate can be applied at 1 mL/min. The polyethylene samples were pretreated by dissolving them in 1,2,4-Trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160°C for 10 hours using a GPC analysis device (PL-GP220), and adjusted to a concentration of 10 mg/10mL. After preparation, it can be supplied in an amount of 200 μL. The values of Mw and Mn can be derived using a calibration curve formed using a polystyrene standard specimen. The weight average molecular weight of polystyrene standard specimens is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g. Nine types of /mol can be used.

The polyethylene may have a weight average molecular weight of 145,000 g/mol to 250,000 g/mol, or 195,000 g/mol to 230,000 g/mol. This means that the molecular weight of polyethylene is high and the content of high molecular weight components is high, which causes the effect of increasing the content of linking molecules, which will be described later.

The polyethylene has a low melt index as described above and a reduced thermal stability index (TSI) as shown in Equation 1 below. This is a characteristic of the polyethylene according to the present invention as the polymer content in the molecular structure increases along with a narrow molecular weight distribution.

[Equation 1]

TSI = (k1×M1) + (k2×M2) + (k3×M3) +k4

In equation 1,

M1 is the ratio (%) of the integral value in the area where Log Mw is 5.0 or more to less than 5.5 to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

M2 is the ratio (%) of the integral value in the area where Log Mw is 5.5 or more to less than 6.0 to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

M3 is the ratio (%) of the integral value of the area where Log Mw is 6.0 or more to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

k1 is 2.15 to 2.65, k2 is -6.95 to -5.65, k3 is -17.4 to -14.2, and k4 is 110.5 to 135.5.

Here, M1, M2, and M3 are values obtained through a molecular weight measurement method using a gel permeation chromatography (GPC) device as described above. Specifically, polyethylene with log Mw on the x axis and dw/dlogMw on the y axis. In the GPC curve graph, the ratio (%) of the integral values of the areas where Log Mw is from 5.0 to less than 5.5, the area from 5.5 to less than 6.0, and the area from 6.0 to the total integral value is shown. Additionally, k1, k2, k3, and k4 are values obtained by the linear regression analysis method. In particular, the values corresponding to the coefficients or additional constants (k1, k2, k3, k4) for M1, M2, and M3 in Equation 1 are based on a large number of data related to molecular weight distribution and thermal stability evaluation of polyethylene as a population. This value was derived through linear regression analysis.

In particular, as the high molecular weight content in the molecular structure of polyethylene increases and the low molecular weight content decreases, the thermal stability of the resin increases. In other words, basically lowering MI ₅ is advantageous in terms of thermal stability. In addition, as the high molecular weight content increases, the number of polymers (tie molecules) connecting the lamellar structure of the crystal increases, thereby better maintaining the crystal structure during the chlorination reaction process and reducing changes in the pore structure of polyethylene powder, which can improve CPE manufacturing productivity. there is. On the other hand, if the low molecular weight content is high, the low molecular weight with high fluidity melts during the chlorination reaction and blocks the pores of the polyethylene powder, which may lengthen the deoxidation and drying process time and reduce productivity.

The Thermal Stability Index (TSI) of Equation 1 may be greater than 0 and less than or equal to 50, or the TSI may be greater than 0 and less than or equal to 40, or greater than 0 and less than or equal to 35.

Specifically, in Equation 1, M1 may be 25 < M1 < 35, M2 may be 10 < M2 < 20, and M3 may be 1 < M3 < 4. More specifically, in Equation 1, M1 may be 28 < M1 < 32, M2 may be 16 < M2 < 18, and M3 may be 2.5 < M3 < 3.6.

Additionally, in Equation 1, k1 may be 2.3 to 2.5, k2 may be -6.5 to -6.1, k3 may be -16.3 to -15.3, and k4 may be 118 to 128. Alternatively, k1 may be 2.35 to 2.45, k2 may be -6.35 to -6.25, k3 may be -15.8 to -15.7, and k4 may be 122.5 to 123.5. Alternatively, k1 may be 2.39 to 2.41, k2 may be -6.3 to -6.34, k3 may be -15.78 to -15.72, and k4 may be 122.8 to 123.1. In particular, k1 may be 2.4, k2 may be -6.33, k3 may be -15.75, and k4 may be 122.98.

Accordingly, the thermal stability index (TSI) of the polyethylene may be a value obtained according to Equation 2 below.

[Equation 2]

TSI = (2.4×M1) + (-6.33×M2) + (-15.75×M3) +122.98

In Equation 2, M1, M2, and M3 are as defined in Equation 1 above.

The Thermal Stability Index (TSI) of polyethylene is determined by measuring the weight average molecular weight (Mw) of polyethylene using gel permeation chromatography (GPC, manufactured by Water) as described above. After creating a log graph for the weight average molecular weight (Mw) of polyethylene, the weight average molecular weight (Mw) content (%) can be measured for each LogMw range and applied to Equation 1 above to obtain it. The specific method for calculating the thermal stability index (TSI) of polyethylene is as described in Test Example 1, which will be described later.

In particular, according to the present invention, through the thermal stability index as described above, the thermal stability of polyethylene and the productivity of chlorinated polyethylene manufacturing can be predicted without directly measuring the yellow index (YI) change rate, which will be described later.

In addition, the polyethylene may have a yellow index (YI) change rate of about 45% or less, or about 0 to about 45%, or about 40% or less, or about 5% to about 40%, or about 35% or less, or about 10% to about 35%, as measured by the method of ASTM D 1238 under the conditions of 250 ℃ and 1 atm after 180 minutes. For reference, the higher the YI value, the closer it is to yellow, the closer the YI value is to 0, the closer it is to a natural color, and the smaller the yellow index change rate of the polyethylene, the higher the heat stability. In addition, the method for measuring the yellow index change rate of the polyethylene is as described in Test Example 1 described below, and the specific measurement method is omitted.

The polyethylene is manufactured by optimizing a specific metallocene catalyst, as will be described later, and is characterized by a low melt index and a high thermal stability index (TSI). As a result, it is possible to provide chlorinated polyethylene with excellent chlorination productivity and thermal stability by increasing the high molecular weight content in the molecular structure.

Meanwhile, according to another embodiment of the invention, a method for producing polyethylene as described above is provided.

The method for producing polyethylene according to the present invention includes at least one first metallocene compound represented by the following formula (1); and polymerizing ethylene by introducing hydrogen gas at 10 ppm to 35 ppm based on the ethylene content in the presence of a catalyst composition comprising at least one second metallocene compound selected from the compounds represented by the following formula (2). may include.

[Formula 1]

(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹ _3-n

In Formula 1,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same or different from each other, and are each independently selected from the group consisting of indenyl and 4,5,6,7-tetrahydro-1-indenyl radicals, and they are C1 to C20 hydrocarbons may be substituted;

R ^a and R ^b are the same or different from each other, and are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C2 to C20 alkoxyalkyl , substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C6 to C10 aryloxy, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C7 to C40 alkylaryl, substituted or unsubstituted C7 to C40 arylalkyl, substituted or unsubstituted C8 to C40 arylalkenyl, or substituted or unsubstituted C2 to C10 alkynyl;

Z ¹ is each independently a halogen atom, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C7 to C40 alkylaryl, substituted or unsubstituted C7 to C40 arylalkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene, substituted or unsubstituted amino group, substituted or unsubstituted C2 to C20 alkylalkoxy, or It is substituted or unsubstituted C7 to C40 arylalkoxy;

n is 1 or 0;

[Formula 2]

In Formula 2,

Q ¹ and Q ² are each independently of each other substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C2 to C20 alkoxyalkyl, or substituted or unsubstituted is aryl of C6 to C20;

A is one or more of a radical containing carbon, germanium, or silicon atoms, or a combination thereof;

M ² is a Group 4 transition metal;

X ^{1 and} Alkylaryl, substituted or unsubstituted C7 to C40 arylalkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene, substituted or unsubstituted amino group, C2 to C20 alkyl Alkoxy, or substituted or unsubstituted C7 to C40 arylalkoxy;

R ¹ to R ¹⁷ are the same or different from each other, and each independently represents hydrogen, a halogen atom, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, or substituted or unsubstituted C1 to C20 alkyl. C20 alkylsilyl, substituted or unsubstituted C1 to C20 silylalkyl, substituted or unsubstituted C1 to C20 alkoxysilyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C2 to C20 alkoxy. Alkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C6 to C10 aryloxy, substituted or unsubstituted C7 to C40 alkylaryl, substituted or unsubstituted C7 to C40 arylalkyl, substituted It is arylalkenyl of C8 to C40, which is substituted or unsubstituted, or alkynyl of C2 to C10, which is substituted or unsubstituted, and two or more of R ¹ to R ¹⁷ adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic or aromatic can form a ring,

At least one of R ¹ to R ⁸ is represented by the following formula (3), and at least one of R ⁹ to R ¹⁷ is represented by the following formula (3),

[Formula 3]

-L ¹ -D ¹

In Formula 3 above,

L ¹ is C1 to C10 alkylene,

D ¹ is C6 to C20 aryl, C4 to C20 cycloalkyl, or C2 to C20 alkoxyalkyl.

The substituents are described in more detail as follows.

The C1 to C20 alkyl groups include straight-chain or branched-chain and cyclic alkyl groups, specifically methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, Heptyl group, octyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. are included, but are not limited thereto.

The C1 to C20 alkylene groups include straight-chain or branched-chain alkylene groups, and specifically include methylene groups, ethylene groups, propylene groups, butylene groups, pentylene groups, and hexylene groups, but are not limited thereto. That is not the case.

The C4 to C20 cycloalkyl group refers to a cyclic alkyl group among the alkyl groups described above, and specifically includes, but is not limited to, cyclobutyl group, cyclopentyl group, and cyclohexyl group.

The C2 to C20 alkenyl group is a straight-chain or branched-chain hydrocarbon with one or more double bonds, and specifically includes an allyl group, an ethenyl group, a propenyl group, a butenyl group, and a pentenyl group, but is not limited thereto. .

The C6 to C20 aryl group includes a monocyclic or condensed ring aryl group, and specifically includes a phenyl group, biphenyl group, naphthyl group, phenanthrenyl group, fluorenyl group, etc., but is not limited thereto.

The C1 to C20 alkoxy groups include methoxy group, ethoxy group, propoxy group, tert-butoxy group, phenyloxy group, cyclohexyloxy group, etc., but are not limited thereto.

The C2 to C20 alkoxyalkyl group is a functional group in which one or more hydrogens of the alkyl group described above are replaced with an alkoxy group, and specifically, methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, and iso-propoxy group. Alkoxyalkyl groups such as ethyl group, iso-propoxyhexyl group, tert-butoxymethyl group, tert-butoxyethyl group, and tert-butoxyhexyl group; Or an aryloxyalkyl group such as a phenoxyhexyl group, but is not limited thereto.

The C2 to C20 alkylalkoxy group is a functional group in which one or more hydrogens of alkoxy are replaced with alkyl as described above, and specifically, methyl methoxy group, methyl ethoxy group, methyl propoxy group, ethyl propoxy group, iso-propoxy group. Examples include, but are not limited to, poxyhexyl group, tert-butoxymethyl group, tert-butoxyethyl group, methylphenyloxy group, and methylcyclohexyloxy group.

The C5 to C20 aryloxy group is a functional group in which one or more carbons of the aryl group as described above are replaced with hydrogen, and specifically includes, but is not limited to, a phenoxy group, a biphenoxy group, and a naphthoxy group. That is not the case.

The C7 to C40 alkylaryl group is a functional group in which one or more hydrogens of the aryl group described above are replaced with an alkyl group, and specifically, methylphenyl group, methylbiphenyl group, methylnaphthyl group, dimethylphenyl group, emethylphenyl group, propylphenyl group, Examples include iso-propylphenyl group and tert-butylphenyl group, but are not limited thereto.

The C7 to C40 arylalkyl group is a functional group in which one or more hydrogens of the alkyl group described above are replaced with an aryl group, and specifically, phenylmethyl group, biphenylmethyl group, naphthylmethyl group, phenylethyl group, biphenylethyl group, naphthylethyl group, Arylalkyl groups such as phenylhexyl groups may be included, but are not limited thereto.

The C8 to C40 arylalkenyl group is a functional group in which one or more hydrogens of the alkenyl group described above are replaced with an aryl group, and specifically, phenylallyl group, phenylethenyl group, phenylpropenyl group, phenylbutenyl group, and phenylpentenyl group. , arylalkenyl groups such as biphenyl allyl group, but are not limited thereto.

The C2 to C10 alkynyl group is a straight-chain or branched-chain hydrocarbon with one or more triple bonds, and specifically includes, but is not limited to, ethynyl group and propynyl.

The C1 to C20 alkylsilyl group or C1 to C20 alkoxysilyl group is a functional group in which 1 to 3 hydrogens of -SiH ₃ are replaced with 1 to 3 alkyl groups or alkoxy groups as described above, specifically methylsilyl group, die Alkylsilyl groups such as methylsilyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group, or dimethylpropylsilyl group; Alkoxysilyl groups such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group, or dimethoxyethoxysilyl group; Alkoxyalkylsilyl groups such as methoxydimethylsilyl group, diethoxymethylsilyl group, or dimethoxypropylsilyl group may be included, but are not limited thereto.

The C1 to C20 silylalkyl group is a functional group in which one or more hydrogens of the alkyl group as described above are replaced with a silyl group, and specifically includes -CH ₂ -SiH ₃ , methylsilylmethyl group, or dimethylethoxysilylpropyl group. , but is not limited to this.

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

In addition, in this specification, two adjacent substituents are connected to each other to form an aliphatic or aromatic ring, which means that the atom(s) of two substituents and the atoms (atoms) to which the two substituents are bonded are connected to each other to form a ring. means that Specifically, adjacent substituents among R ¹ to R ¹⁷ , such as R ² and R ³ or R ³ and R ⁴ , may be connected to each other to form an aromatic ring.

The above-mentioned substituents are optionally hydroxy groups within the range of having the same or similar effect as the desired effect; halogen; Alkyl group or alkenyl group, aryl group, alkoxy group; an alkyl group or alkenyl group, an aryl group, or an alkoxy group containing one or more heteroatoms from groups 14 to 16; silyl group; Alkylsilyl group or alkoxysilyl group; Phosphine group; phosphide group; Sulfonate group; and may be substituted with one or more substituents selected from the group consisting of a sulfone group.

The sulfonate group has the structure of -O-SO ₂ -R', where R' may be a C1 to C20 alkyl group. Specifically, the C1 to C20 sulfonate group may include a methanesulfonate group or a phenylsulfonate group, but is not limited thereto.

The Group 4 transition metals include titanium (Ti), zirconium (Zr), and hafnium (Hf), but are not limited thereto.

Meanwhile, as described above, when the ethylene polymerization process is performed using a hybrid supported catalyst containing the metallocene compounds of Formula 1 and Formula 2, thermal stability is required to achieve excellent productivity in the chlorination process when producing chlorinated polyolefin. Excellent polyolefin can be produced effectively.

Specifically, in the hybrid supported catalyst, the first metallocene compound contains long chain branches and is easy to produce low molecular weight polyethylene, and the second metallocene compound is contained in a smaller amount than the first metallocene compound. It is easy to produce polyethylene with a relatively high molecular weight and long chain branches. In particular, when there are many long chain branches in the polymer and the molecular weight is high, the melt strength increases. However, in the case of the first metallocene compound, there are many long chain branches but low molecular weight, so there is a limit to improving this.

In the polyethylene polymerization process of the present invention, a first metallocene compound that produces a polymer with relatively many long chain branches and a low molecular weight and a second metallocene compound that produces a polymer with relatively few long chain branches and a high molecular weight are used. By using a hybrid supported catalyst, chlorination productivity can be improved by effectively controlling molecular weight distribution and improving thermal stability while maintaining excellent high molecular weight. By hybridizing the two types of metallocene compounds, the long chain branch present in the polymer is located at a relatively low molecular weight, thereby improving molecular weight distribution and thermal stability.

More specifically, the first metallocene compound represented by Formula 1 has a structure containing an indenyl or tetrahydro indenyl series ligand, and when a catalyst of this structure is polymerized, there is a small amount of long chain branching and the molecular weight is A polymer with a relatively narrow distribution (PDI, MWD, Mw/Mn) can be obtained.

Specifically, in the structure of the first metallocene compound represented by Formula 1, indenyl, or 4,5,6,7-tetrahydro-1-indenyl radical ligand is, for example, involved in polyethylene polymerization activity. It can have an impact.

Additionally, in Formula 1, M ¹ is Ti, Zr, or Hf; R ^a and R ^b are the same or different from each other, and are each independently hydrogen, C1 to C20 alkyl, C2 to C20 alkoxyalkyl, or C7 to C40 arylalkyl; Z ¹ may be a halogen atom. Alternatively, in Formula 1, Cp ¹ and Cp ² are each independently indenyl or 4,5,6,7-tetrahydro-1-indenyl; R ^a and R ^b are each independently hydrogen, methyl, or tert-butoxy hexyl; M ¹ is Zr; Z ¹ may be a halogen atom such as chlorine.

Specific examples of the metallocene compound of Formula 1 include bis(3-(6-(tert-butoxy)hexyl)-1H-inden-1-yl)zirconium(IV) chloride, or bis(3-(6- (tert-butoxy)hexyl)-4,5,6,7-tetrahydro-1H-inden-1-yl)zirconium(IV) chloride, etc., but is not limited thereto.

The first metallocene compound represented by Formula 1 can be synthesized by applying known reactions. Specifically, it can be manufactured by preparing a ligand compound through various synthesis processes and then performing metallation by adding a metal precursor compound, but it is not limited to this, and the examples can be referred to for more detailed synthesis methods. .

The method for producing polyethylene according to the present invention is to increase the melt index of polyethylene by using at least one first metallocene compound represented by Chemical Formula 1 as described above together with at least one second metallocene compound described later. (MI ₅ ), molecular weight distribution (Mw/Mn), and thermal stability index (TSI) can be optimized simultaneously, thereby producing chlorinated polyethylene with excellent chlorination productivity and thermal stability.

Meanwhile, the second metallocene compound may be represented by Formula 2.

Specifically, the second metallocene compound represented by Formula 2 includes a specific substituent, such as a benzyl group, in the ligand, and the ligand has a structure in which the ligand is cross-linked by Si or the like. By polymerizing a catalyst of this structure, a polymer with a small amount of long chain branches and a relatively narrow molecular weight distribution (PDI, MWD, Mw/Mn) can be obtained.

Specifically, the molecular weight of the polyethylene produced can be easily adjusted by adjusting the degree of steric hindrance effect according to the type of substituted functional group of the ligand within the structure of the second metallocene compound represented by Formula 2.

Specifically, in Formula 2, M ² is Ti, Zr, or Hf; A is carbon, germanium, or silicon; Q ¹ and Q ² are each independently C1 to C20 alkyl, or C2 to C20 alkoxyalkyl; R ² or R ⁷ is represented by the following formula (3a), R ¹⁰ or R ¹⁶ is represented by the following formula (3a), and the remainder of R ¹ to R ¹⁷ is hydrogen, halogen, or C1 to C20 alkyl; X ¹ and X ² may each independently be a halogen atom.

[Formula 3a]

-L ² -D ²

In Formula 3a,

L ² is C1 to C10 alkylene, and D ² is C6 to C20 aryl or C4 to C20 cycloalkyl.

Alternatively, in Formula 2, M ² is Zr; A is silicon; Q ¹ and Q ² are each independently methyl, ethyl, propyl, or tert-butoxyhexyl; R ² or R ⁷ is represented by the following formula (3b), R ¹⁰ or R ¹⁶ is represented by the following formula (3b), and the remainder among R ¹ to R ¹⁷ is hydrogen; X ¹ and X ² may each independently be a halogen atom. In particular, R ² and R ¹⁶ are represented by the following formula 3b, and R ¹ , R ³ to R ¹⁵ , and R ¹⁷ may be hydrogen.

[Formula 3b]

-L ³ -D ³

In Formula 3b,

L ³ is C1 to C2 alkylene, and D ³ is C6 to C8 aryl or C5 to C6 cycloalkyl.

Meanwhile, a specific example of the second metallocene compound represented by Formula 2 is dichloro[[[6-(tert-butoxy)hexyl]methylsilylene]bis[(4a,4b,8a,9,9a-η )-2-(cyclopentylmethyl)-9H-fluoren-9-ylidene]]zirconium, dichloro[[[6-(tert-butoxy)hexyl]methylsilylene]bis[(4a,4b,8a, 9,9a-η)-2-(phenylmethyl)-9H-fluoren-9-ylidene]]zirconium, or dichloro[[[6-(tert-butoxy)hexyl]methylsilylene]bis[(4a ,4b,8a,9,9a-η)-2-(cyclohexylmethyl)-9H-fluoren-9-ylidene]]zirconium, etc., but is not limited thereto.

The second metallocene compound represented by Formula 2 can be synthesized by applying known reactions. Specifically, it can be manufactured by preparing a ligand compound through various synthesis processes and then performing metallation by adding a metal precursor compound, but it is not limited to this, and the examples can be referred to for more detailed synthesis methods. .

The metallocene catalyst used in the present invention may be supported on a carrier together with a cocatalyst compound.

In the supported metallocene catalyst according to the present invention, the cocatalyst supported on the carrier to activate the metallocene compound is an organometallic compound containing a Group 13 metal, which polymerizes olefins under a general metallocene catalyst. There is no particular limitation as long as it can be used when doing so.

The cocatalyst is an organometallic compound containing a Group 13 metal, and is not particularly limited as long as it can be used when polymerizing ethylene under a general metallocene catalyst.

Specifically, the cocatalyst may be one or more selected from the group consisting of compounds represented by the following formulas 4 to 6:

[Formula 4]

-[Al(R ¹⁸ )-O] _c -

In Formula 4 above,

R ¹⁸ is each independently halogen, C _1-20 alkyl, or C _1-20 haloalkyl,

c is an integer greater than or equal to 2,

[Formula 5]

D(R ¹⁹ ) ₃

In Formula 5 above,

D is aluminum or boron,

R ¹⁹ is each independently hydrogen, halogen, C _1-20 hydrocarbyl, or C _1-20 hydrocarbyl substituted with halogen,

[Formula 6]

[LH] ⁺ [Q(E) ₄ ] ^- or [L] ⁺ [Q(E) ₄ ] ^-

In Formula 6 above,

L is a neutral or cationic Lewis base,

[LH] ⁺ is Bronsted acid,

Q is ^{Br 3+} or ^{Al 3+} ,

E is each independently C _6-20 aryl or C _1-20 alkyl, wherein the C _6-20 aryl or C _1-20 alkyl is unsubstituted or selected from halogen, C _1-20 alkyl, C _1-20 alkoxy and It is substituted with one or more substituents selected from the group consisting of phenoxy.

The compound represented by Formula 4 may be, for example, an alkyl aluminoxane such as modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, etc.

The alkyl metal compound represented by the formula 5 is, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloroaluminum, dimethyl isobutyl aluminum, dimethyl ethyl aluminum, diethyl chloro. Aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl It may be aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc.

Compounds represented by Formula 6 include, for example, triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (p- Tolyl) boron, tripropylammonium tetra(p-tolyl) boron, triethylammonium tetra(o,p-dimethylphenyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra (p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylaniliniumtetraphenyl boron, N, N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetra Phenylboron, Triethylammonium Tetraphenyl Aluminum, Tributylammonium Tetraphenyl Aluminum, Trimethylammonium Tetraphenyl Aluminum, Tripropylammonium Tetraphenyl Aluminum, Trimethylammonium Tetra(p-Tolyl) Aluminum, Tripropylammonium Tetra (p-tolyl) aluminum, triethylammonium tetra(o,p-dimethylphenyl) aluminum, tributylammonium tetra(p-trifluoromethylphenyl) aluminum, trimethylammonium tetra(p-trifluoromethylphenyl) aluminum. ,Tributylammonium Tetrapentafluorophenyl Aluminum, N,N-Diethylanilinium Tetraphenyl Aluminum, N,N-Diethylanilinium Tetraphenyl Aluminum, N,N-Diethylanilinium Tetrapentaflo Lophenylaluminum, diethylammonium tetrapentafluorophenyl aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, triphenylcarboniumtetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenyl It may be carbonium tetra (p-trifluoromethylphenyl) boron, triphenyl carbonium tetrapentafluorophenyl boron, etc.

The supported amount of this cocatalyst may be 5 mmol to 20 mmol based on 1 g of carrier.

In the supported metallocene catalyst according to the present invention, a carrier containing a hydroxy group on the surface can be used as the carrier, and preferably has a highly reactive hydroxy group and a siloxane group that has been dried to remove moisture from the surface. Any carrier can be used.

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

The drying temperature of the carrier is preferably 200 to 800°C, more preferably 300 to 600°C, and most preferably 300 to 400°C. If the drying temperature of the carrier is less than 200 ℃, there is too much moisture, so the moisture on the surface reacts with the cocatalyst. If it exceeds 800 ℃, the pores on the surface of the carrier merge, reducing the surface area, and there are many hydroxyl groups on the surface. This is undesirable because it disappears and only siloxane residues remain, reducing the number of reaction sites with the cocatalyst.

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

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

In the supported metallocene catalyst according to the present invention, the mass ratio of the total transition metal contained in the metallocene catalyst to the carrier may be 1:10 to 1:1000. When the carrier and metallocene compound are included in the above mass ratio, the optimal shape can be exhibited. Additionally, the mass ratio of co-catalyst compound to carrier may be 1:1 to 1:100.

The ethylene polymerization reaction can be performed using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

In particular, the polyethylene according to the present invention includes at least one first metallocene compound represented by the above formula (1); And it can be prepared by homopolymerizing ethylene in the presence of at least one second metallocene compound selected from the compounds represented by Formula 3 above.

The weight ratio of the first metallocene compound and the second metallocene compound (first metallocene compound: second metallocene compound) is 25:75 to 35:65, or 28:72 to 32:68. You can. The weight ratio of the catalyst precursor may be as described above in terms of implementing a molecular structure with narrow particle distribution and increased polymer content so as to produce chlorinated polyethylene with excellent chlorination productivity and thermal stability. In particular, when the weight ratio of the first metallocene compound and the second metallocene compound is applied within the above-mentioned range, the amount of hydrogen input in the polymerization process can be reduced to about 35 ppm or less, and the wax content can be reduced to 10 ppm. It can be kept below %. The wax content can be measured by the volume ratio occupied by wax by separating the polymerization product using a centrifugal separation device, sampling 100 mL of the remaining hexane solvent, and settling for 2 hours.

In addition, the method for producing polyethylene according to the present invention can be produced in the presence of a metallocene catalyst as described above while adding hydrogen gas content in an optimal range compared to ethylene. At this time, hydrogen gas should be introduced in an amount of 10 ppm to 35 ppm relative to ethylene, or hydrogen gas may be added in an amount of 10 ppm to 20 ppm.

And, the polymerization temperature may be 80°C to 84°C, or 80°C to 81°C. Additionally, the polymerization pressure may be 7.0 kg/cm ² to 9.0 kg/cm ² , or 7.0 kg/cm ² to 8.0 kg/cm ² .

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

Meanwhile, according to another embodiment of the invention, chlorinated polyethylene (CPE) using polyethylene as described above is provided.

Chlorinated polyethylene according to the present invention can be produced by polymerizing ethylene in the presence of the above-described supported metallocene catalyst and then reacting this with chlorine.

The reaction with chlorine can be performed by dispersing the prepared polyethylene with water, an emulsifier and a dispersant, and then adding a catalyst and chlorine.

Polyether or polyalkylene oxide can be used as the emulsifier. The dispersant may be a polymer salt or an organic acid polymer salt, and the organic acid may be methacrylic acid or acrylic acid.

The catalyst may be a chlorination catalyst used in the industry, and for example, benzoyl peroxide may be used. The chlorine can be used alone or mixed with an inert gas.

The chlorination reaction is preferably carried out at about 60°C to about 150°C, or about 70°C to about 145°C, or about 80°C to about 140°C, and the reaction time is about 10 minutes to about 10 hours, or about 1 hours to about 9 hours, or about 2 hours to about 8 hours is preferred.

Chlorinated polyethylene produced by the above reaction can be additionally subjected to a neutralization process, a washing process, and/or a drying process, and thus can be obtained in powder form.

For example, the chlorinated polyethylene may have a chlorine content of about 20% by weight to about 45% by weight, about 31% by weight to about 40% by weight, or about 33% by weight to about 38% by weight. Here, the chlorine content of the chlorinated polyethylene can be measured using combustion ion chromatography (Combustion IC, Ion Chromatography) analysis. As an example, the combustion ion chromatography analysis method uses a combustion IC (ICS-5000/AQF-2100H) device equipped with an IonPac AS18 (4 x 250 mm) column, an internal device temperature (Inlet temperature) of 900 ℃, and an external device Outlet temperature: It can be measured under a flow rate of 1 mL/min using KOH (30.5 mM) as an eluent at a combustion temperature of 1000°C.

For example, the chlorinated polyethylene may be random chlorinated polyethylene.

Chlorinated polyethylene manufactured according to the present invention has excellent chemical resistance, weather resistance, flame retardancy, processability, and impact strength reinforcing effect, and is widely used as an impact reinforcing agent for PVC pipes and window profiles.

In addition, the method of manufacturing a molded article from chlorinated polyethylene according to the present invention can be a conventional method in the art. For example, a molded product can be manufactured by roll-mill compounding the chlorinated polyethylene and extruding it.

Below, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are provided only to make the present invention easier to understand, and the content of the present invention is not limited thereto.

[Manufacture of catalyst precursor]

Synthesis example One: [ ^t Bu-O-(CH ₂ ) ₆ -C ₉ H ₆ ] ₂ ZrCl ₂ of synthesis

t-Butyl-O-(CH ₂ ) ₆ -Cl was prepared using 6-chlorohexanol by the method suggested in the literature (Tetrahedron Lett. 2951 (1988)), and then reacted with indene. t-Butyl-O-(CH ₂ ) ₆ -C ₉ H ₇ was obtained (yield 90%). In addition, t-Butyl-O-(CH ₂ ) ₆ -C ₉ H ₇ was dissolved in THF at -78°C, normal butyllithium (n-BuLi) was slowly added, the temperature was raised to room temperature, and reaction was performed for 8 hours. . The solution was again slowly added to the previously synthesized lithium salt solution in a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol)/THF (30 mL) at -78°C. and reacted for further 6 hours at room temperature.

All volatile substances were vacuum dried, and hexane solvent was added to the obtained oily liquid and filtered. After vacuum drying the filtered solution, hexane was added to induce precipitate at low temperature (-20°C). The obtained precipitate was filtered at low temperature to obtain [ ^t Bu-O-(CH ₂ ) ₆ -C ₉ H ₆ ] ₂ ZrCl ₂ compound in the form of a white solid (88% yield).

^1H NMR (300 MHz, CDCl ₃ ): 0.84-1.63 (38H, m), 2.61-2.76 (1H, m), 2.87-2.97 (1H, m), 3.24-3.33 (4H, m), 5.66 (0.5) H, d), 5.80 (0.5H, d), 6.04 (0.5H, d), 6.28 (0.5H, d), 7.18-7.63 (8H, m)

Synthesis example 2: [ ( tert -Bu-O-(CH ₂ ) ₆ )MeSi(9-C ₂₀ H ₁₄ ) ₂ ]ZrCl ₂ of synthesis

1.0 mole of tert -Bu-O-(CH ₂ ) ₆ MgCl solution, a Grignard reagent, was obtained from the reaction between tert -Bu-O-(CH ₂ ) ₆ Cl compound and Mg(0) in THF solvent. The prepared Grignard compound was added to a flask containing MeSiCl ₃ compound (176.1 mL, 1.5 mol) and THF (2.0 mL) at -30°C, stirred at room temperature for more than 8 hours, and the filtered solution was vacuum-filtered. After drying, the compound tert -Bu-O-(CH ₂ ) ₆ SiMeCl ₂ was obtained (yield 92%).

Dissolve 2-(Benzyl)-9H-fluorene (Bn-Flu) (5.13 g, 20 mmol) in 100 mL of diethyl ether in a dryice/acetone bath at -20°C and add 9.2 mL (23 mmol) of n-BuLi (2.5). M in Hexane) was slowly added and stirred at room temperature for 6 hours to prepare a 2-(Benzyl)-9H-fluorenyl lithium solution. After the stirring was terminated, the reactor temperature was cooled to -30 ℃, and tert -Bu-O-(CH ₂ ) ₆ SiMeCl ₂ (2.71 g, 10 mmol) dissolved in hexane (50 mL) at -30 ℃ was added to the solution. The 2-(Benzyl)-9H-fluorenyl lithium solution prepared above was slowly added over 1 hour. After stirring at room temperature for more than 8 hours, water was added for extraction and drying (evaporation) to obtain a heavy compound (4.96 g, yield 69.8%). The structure of the ligand was confirmed through ¹ H-NMR.

¹ H NMR (500 MHz, CDCl ₃ ): (-0.49)-(-0.35) (3H, m), 0.10-1.31 (19H, m), 3.16-3.21 (2H, m), 3.79 (1H, s) , 3.91-3.96(5H, m), 7.00-7.35 (24H, m)

Dissolve (6-( tert -butoxy)hexyl)bis(2-(benzyl)-9H-fluoren-9-yl)(methyl)silane (4.96 g, 7 mmol) in 100 mL of toluene at -20°C, and add MTBE 3.3. Slowly add 6.1 mL (2.2 eq) of n-BuLi (2.5 M in Hexane) to the solution to which L (4.0 eq) was added, raise the temperature to room temperature and react for more than 8 hours, then dilithium salt prepared above at -20°C. (dilithium salts) was slowly added to the slurry solution of ZrCl ₄ (THF) ₂ (2.63 g, 7 mmol)/toluene (100 mL) and reacted at room temperature for an additional 8 hours. The precipitate was filtered and washed several times with hexane to obtain [( tert -Bu-O-(CH ₂ ) ₆ )MeSi(9-C ₂₀ H ₁₄ ) ₂ ]ZrCl ₂ compound in solid form (3.58 g, yield 58.9%). ).

^1H NMR (500MHz, CDCl ₃ ): 1.16-1.20 (9H, m), 1.34 (3H, s), 1.45-1.92 (10H, m), 3.36-3.38(2H, m), 3.86-3.96(4H, m), 6.90-7.81 (24H, m)

comparison Synthesis example One: [ ^t Bu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ of synthesis

t-Butyl-O-(CH ₂ ) ₆ -Cl was prepared using 6-chlorohexanol by the method suggested in the literature (Tetrahedron Lett. 2951 (1988)), and NaCp was reacted with it. t-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80 ℃ / 0.1 mmHg). Additionally, t-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78°C, normal butyllithium (n-BuLi) was slowly added, the temperature was raised to room temperature, and reaction was performed for 8 hours. . The previously synthesized lithium salt solution was slowly added to the suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol)/THF (30 ml) at -78°C, and then allowed to cool at room temperature. The reaction was further performed for 6 hours.

All volatile substances were vacuum dried, and hexane solvent was added to the obtained oily liquid and filtered. After vacuum drying the filtered solution, hexane was added to induce precipitate at low temperature (-20°C). The obtained precipitate was filtered at low temperature to obtain [ ^t Bu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound in the form of a white solid (yield 92%).

　

¹ H NMR (300 MHz, CDCl ₃ ): 6.28 (t, J = 2.6 Hz, 2 H), 6.19 (t, J = 2.6 Hz, 2 H), 3.31 (t, 6.6 Hz, 2 H), 2.62 ( t, J = 8 Hz), 1.7 - 1.3 (m, 8 H), 1.17 (s, 9 H)

comparison Synthesis example 2: [ ( tert -Bu-O-(CH ₂ ) ₆ )(CH ₃ )Si(C ₅ (CH ₃ ) ₄ )( ^t Bu-N)]TiCl ₂ of synthesis

After adding 50 g of Mg(s) to a 10 L reactor at room temperature, 300 mL of THF was added. After adding about 0.5 g of I2, the reactor temperature was maintained at 50°C. After the reactor temperature was stabilized, 250 g of 6-t-butoxyhexyl chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. It was observed that the reactor temperature increased by about 4 to 5 °C as 6-t-butoxyhexyl chloride was added. The mixture was stirred for 12 hours while continuously adding 6-t-butoxyhexyl chloride. After 12 hours of reaction, a black reaction solution was obtained. After taking 2 mL of the resulting black solution, water was added to obtain an organic layer, and 6-t-butoxyhexane was confirmed through 1H-NMR. It was confirmed from the 6-t-butoxyhexane that the Gringanrd reaction proceeded well. Thus, 6-t-butoxyhexyl magnesium chloride was synthesized.

　

After adding 500 g of MeSiCl ₃ and 1 L of THF to the reactor, the temperature of the reactor was cooled to -20°C. 560 g of the synthesized 6-t-butoxyhexyl magnesium chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. After the feeding of the Grignard reagent was completed, the reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, it was confirmed that white MgCl2 salt was produced. 4 L of hexane was added and the salt was removed through labdori to obtain a filter solution. The obtained filter solution was added to the reactor, and hexane was removed at 70°C to obtain a light yellow liquid. The obtained liquid was confirmed to be the desired methyl(6-t-butoxy hexyl)dichlorosilane {Methyl(6-t-butoxy hexyl)dichlorosilane} compound through 1H-NMR.

　

1H-NMR (CDCl3): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H)

1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, and the temperature of the reactor was cooled to -20°C. n-BuLi 480 mL was added to the reactor at a rate of 5 mL/min using a feeding pump. After adding n-BuLi, the reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, an equivalent amount of methyl(6-t-butoxy hexyl)dichlorosilane (326 g, 350 mL) was quickly added to the reactor. The reactor temperature was slowly raised to room temperature while stirring for 12 hours, and then the reactor temperature was cooled to 0° C. and then 2 equivalents of t-BuNH ₂ was added. The reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, THF was removed, 4 L of hexane was added, and a filter solution from which salts were removed was obtained through labrador. After adding the filter solution back to the reactor, hexane was removed at 70°C to obtain a yellow solution. The yellow solution obtained was confirmed to be a methyl(6-t-butoxyhexyl)(tetramethylCpH)t-butylaminosilane compound through ¹ H-NMR. did.

　

TiCl ₃ (THF) ₃ (10 mmol) was synthesized in a THF solution from n-BuLi and the ligand dimethyl(tetramethylCpH)t-Butylaminosilane. ) was applied quickly. The reaction solution was stirred for 12 hours while slowly raising the temperature from -78°C to room temperature. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature and stirred for 12 hours. After stirring for 12 hours, a dark black solution with a blue tinge was obtained. After THF was removed from the resulting reaction solution, hexane was added and the product was filtered. After removing hexane from the filter solution, the desired ([methyl(6-t-buthoxyhexyl)silyl(η5-tetramethylCp)(t-Butylamido)]TiCl ₂ ) was obtained from ¹ H-NMR. [( tert -Bu-O-(CH ₂ ) ₆ )(CH ₃ )Si(C ₅ (CH ₃ ) ₄ )( ^t Bu-N)]TiCl ₂ was confirmed.

　

¹ H-NMR (CDCl ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 ~ 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H) , 0.7 (s, 3H)

[Manufacture of supported catalyst]

Manufacturing example 1: Preparation of supported catalyst

5.0 kg of toluene solution was added to a 20 L sus high pressure reactor, and the reactor temperature was maintained at 40°C. 1000 g of silica (SP948, manufactured by Grace Davison) dehydrated by applying vacuum for 12 hours at a temperature of 600° C. was added to the reactor and the silica was sufficiently dispersed. Then, 55 g of the metallocene compound of Synthesis Example 1 was dissolved in toluene. It was added and stirred at 40°C at 200 rpm for 2 hours to react. Afterwards, stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decantated.

2.5 kg of toluene was added to the reactor, 9.4 kg of 10 wt% methylaluminoxane (MAO)/toluene solution was added, and the mixture was stirred at 40°C and 200 rpm for 12 hours. After the reaction, stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decantated. 3.0 kg of toluene was added and stirred for 10 minutes, then stirring was stopped, settling was performed for 30 minutes, and the toluene solution was decantated.

3.0 kg of toluene was added to the reactor, and 142.3 g of the metallocene compound of Synthesis Example 2 was dissolved in 1 L of toluene solution and added to the reactor, and the mixture was stirred at 40°C and 200 rpm for 2 hours to react. At this time, the ratio between the metallocene compound of Synthesis Example 1 and the metallocene compound of Synthesis Example 2 was 28:72 based on weight. After lowering the reactor temperature to room temperature, stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decantated.

2.0 kg of toluene was added to the reactor and stirred for 10 minutes, then stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decantated.

3.0 kg of hexane was added to the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. 1 kg-SiO ₂ hybrid supported catalyst was prepared by drying under reduced pressure at 40°C for 4 hours.

comparison Manufacturing example 1: Preparation of supported catalyst

Prepared in the same manner as Preparation Example 1, except that the metallocene compound of Comparative Synthesis Example 1 was used instead of the metallocene compound of Synthesis Example 1, and the metallocene compound of Comparative Synthesis Example 2 was used instead of the metallocene compound of Synthesis Example 2. Using the locene compound, a hybrid supported catalyst was prepared at a ratio of 28:72 by weight between the metallocene compound of Comparative Synthesis Example 1 and the metallocene compound of Comparative Synthesis Example 2.

[Manufacture of polyethylene]

Example 1-1

The supported catalyst prepared in Preparation Example 1 was introduced into a single slurry polymerization process to produce high-density polyethylene.

First, 23 kg/hr of hexane, 10 kg/hr of ethylene, and 0.2 g/hr of hydrogen, i.e., 20 ppm of hydrogen compared to ethylene, and triethylaluminum (TEAL) were added to a single-CSTR reactor with ^a capacity of 0.2 m 3 ) were respectively injected at a flow rate of 130 cc/hr, and the hybrid supported metallocene catalyst according to Preparation Example 1 was injected at 2 g/hr (170 μmol/hr). At this time, the reactor was maintained at 80° C. and the pressure was maintained at 7.0 to 7.5 kg/cm ² , and continuous reaction was performed in the form of a hexane slurry, followed by solvent removal and drying processes to prepare high-density polyethylene in powder form.

Example 1-2

High-density polyethylene in powder form was manufactured in the same manner as in Example 1-1, except that the hydrogen input amount was 0.1 g/hr, that is, the hydrogen input amount was 10 ppm compared to ethylene.

Comparative example 1-1

A commercially available high-density polyethylene (HDPE) product (CE6040K, LG Chem) prepared using a Ziegler-Natta catalyst and having a melt index (MI ₅ , 190° C., 5 kg) of 0.5 g/10 min was prepared in Comparative Example 1-1. .

Comparative example 1-2

It was prepared in the same manner as Example 1-1, but instead of the supported catalyst of Preparation Example 1, the hybrid supported metallocene catalyst prepared in Comparative Preparation Example 1 was injected at 2 g/hr (170 μmol/hr), and hydrogen High-density polyethylene in powder form was manufactured by varying the input amount of 1.0 g/hr, that is, 100 ppm of hydrogen compared to ethylene.

Comparative example 1-3

High-density polyethylene in powder form was manufactured in the same manner as in Comparative Example 1-2, except that the hydrogen input was 0.2 g/hr, that is, 20 ppm of hydrogen compared to ethylene.

Test example One

The physical properties of the polyethylene prepared in Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 1 below.

1) Melt index (MI, g/10 minutes): The melt index (MI ₅ ) was measured using the method of ASTM D 1238 at a temperature of 190 ℃ and a load of 5 kg, and the weight of the polymer melted for 10 minutes ( It is expressed as g).

2) Density: The density (g/cm ³ ) of polyethylene was measured by the method of ASTM D 1505.

3) Weight average molecular weight (M _W ) and molecular weight distribution (MWD, polydispersity index): Using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water), the weight average molecular weight (Mw) and number average molecular weight of polyethylene ( Mn) was measured, and the molecular weight distribution (MWD) was calculated by dividing the weight average molecular weight by the number average molecular weight.

Specifically, a Waters PL-GPC220 instrument was used as a gel permeation chromatography (GPC) device, and a 300 mm long column from Polymer Laboratories PLgel MIX-B was used. At this time, the measurement temperature was 160°C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL/min. The polyethylene samples according to the Examples and Comparative Examples were pretreated by melting them in 1,2,4-Trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160°C for 10 hours using a GPC analysis device (PL-GP220). It was prepared at a concentration of 10 mg/10mL and then supplied in an amount of 200 μL. The values of Mw and Mn were derived using a calibration curve formed using a polystyrene standard specimen. The weight average molecular weight of polystyrene standard specimens is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g. Nine types of /mol were used.

4) Thermal Stability Index (TSI): The weight average molecular weight (Mw) of polyethylene is measured as described above using a Waters PL-GPC220 gel permeation chromatography (GPC) device. After creating a log graph for weight average molecular weight (Mw), the thermal stability index (TSI) of polyethylene was calculated from this according to Equation 1 below.

[Equation 1]

TSI = (k1×M1) + (k2×M2) + (k3×M3) +k4

In equation 1,

M1 is the ratio (%) of the integral value in the area where Log Mw is 5.0 or more to less than 5.5 to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

M2 is the ratio (%) of the integral value in the area where Log Mw is 5.5 or more to less than 6.0 to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

M3 is the ratio (%) of the integral value of the area where Log Mw is 6.0 or more to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,

k1 is 2.15 to 2.65, k2 is -6.95 to -5.65, k3 is -17.4 to -14.2, and k4 is 110.5 to 135.5.

In particular, k1, k2, k3, and k4 are values obtained by linear regression analysis. Specifically, in Test Example 1, k1 is 2.4, k2 is -6.33, k3 is -15.75, and k4 is 122.98.

In addition, M1, M2, and M3 are values obtained through a molecular weight measurement method using a gel permeation chromatography (GPC) device as described above, and the specific values are as shown in Table 1 below.

Specifically, the thermal stability index (TSI) for the polyethylene of Examples and Comparative Examples can be obtained according to the following equation 1-1 after measuring M1, M2, and M3 in the same manner as described above, The values obtained according to 2, rounded to two decimal places, are shown in Table 1 below.

[Equation 2]

TSI = (2.4×M1) + (-6.33×M2) + (-15.75×M3) +122.98

In Equation 2, M1, M2, and M3 are as defined in Equation 1 above.

5) Yellow index change rate (ΔY.I, YI change rate, %): The yellow index (YI) change rate for polyethylene was measured according to the method of ASTM D 1925.

Specifically, polyethylene specimens were prepared using Collin's COLLIN P200E (hot press) machine. Polyethylene was melted in a mold measuring 80 mm wide, 80 mm long, and 2 mm thick under the conditions of 190°C, 10 minutes, and 30 bar, and then cooled at a rate of 5°C/min. After 24 hours at room temperature, the initial yellow index (YI) value of the prepared polyethylene specimen was measured using a Spectro photo meter CM-700d from KONICA MINOTA. After measuring the initial YI value of the polyethylene specimen after 180 minutes at 250°C and 1 atm, the YI value was remeasured, and ΔY.I (%) of polyethylene was obtained from this. For reference, the higher the YI value, the closer to yellow, the closer the YI value is to 0, the closer to natural color, and the smaller the yellow index change rate of polyethylene, the higher the thermal stability.

Example Comparative example 1-1 1-2 1-1 1-2 1-3 catalyst Manufacturing Example 1 Manufacturing Example 1 Z/N Comparative Manufacturing Example 1 Comparative Manufacturing Example 1 First metallocene compound Synthesis Example 1 Synthesis Example 1 - Comparative Synthesis Example 1 Comparative Synthesis Example 1 Secondary metallocene compound Synthesis Example 2 Synthesis Example 2 - Comparative Synthesis Example 2 Comparative Synthesis Example 2 H ₂ (g/hr) 0.2 0.1 - 1.0 0.2 H ₂ input amount compared to ethylene (ppm) 20 10 - 100 20 MI (5kg, 190℃, g/10min) 0.3 0.2 0.5 1.6 0.8 Density (g/cm ³ ) 0.951 0.951 0.952 0.951 0.951 Mw (×10 ³ g/mol) 215 229 217 153 180 Molecular weight distribution (Mw/Mn) 4.6 4.2 4.6 3.1 3.6 LogMw (%) 5.0~5.5 28.7 31.3 32.6 33.0 30.9 5.5~6.0 17.1 17.9 15.0 8.7 11.5 ≥6.0 3.2 3.5 3.5 1.5 2.4 TSI 33.2 29.7 51.1 123.5 86.5 ΔY.I (%) 33.3 30.2 51.5 123.8 88.5

As shown in Table 1, compared to the comparative examples, the ΔY.I (%) of the examples decreased, indicating that the thermal stability of polyethylene was excellent. In particular, compared to the comparative examples, it was confirmed that the thermal stability of the examples was superior as the high molecular weight content of LogMw 5.5 to 6.0 and 6.0 or more increased, or the low molecular weight content of LogMw 5.5 or less decreased. And, by formulating this, it was possible to quantify the thermal stability of the resin and predict CPE productivity just by GPC analysis, and based on this, high-density polyethylene suitable for excellent CPE productivity was developed.

Test example 2

Chlorinated polyethylene was manufactured using the polyethylene prepared in Examples and Comparative Examples.

[Manufacture of chlorinated polyethylene]

Add 5000 L of water and 550 kg of high-density polyethylene prepared in Example 1-1 to the reactor, then add sodium polymethacrylate as a dispersant, oxypropylene and oxyethylene copolyether as emulsifiers, and benzoyl peroxide as a catalyst. After raising the temperature from 80°C to 132°C at a rate of 17.3°C/hr, gaseous chlorine was injected for 3 hours at a final temperature of 132°C to perform chlorination. At this time, gaseous chlorine was injected while the temperature was raised and the pressure in the reactor was maintained at 0.3 MPa, and the total amount of chlorine introduced was 610 kg. The chlorinated reactant was neutralized by adding NaOH for 4 hours, washed again with running water for 4 hours, and finally dried at 120° C. to prepare chlorinated polyethylene in powder form.

In addition, the polyethylene produced in Example 1-2 and Comparative Examples 1-1 to 1-2 was also manufactured in powder form by the same method as above.

As described above, using the polyethylene prepared in Examples 1-1 to 1-2 and Comparative Examples 1-1 to 1-2, the following Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2 For the process of producing -2 chlorinated polyethylene (CPE), the chlorination productivity of CPE was evaluated in the following manner, and the results are shown in Table 2 below.

1) Chlorination productivity of CPE: The evaluation of CPE productivity was conducted using the polyethylene (CE604K) of Comparative Example 1-1, an existing commercial product, based on 4 hours of drying time at 120°C during the manufacturing process of chlorinated polyethylene (100%). In examples and comparative examples, drying time was evaluated as a relative ratio.

In particular, in terms of CPE productivity, if the drying time exceeds 4 hours, the CPE particle morphology is modified and porosity is reduced, considering the raw material input time, chlorination process time, and transport time. The existing continuous process is judged to be difficult, and the amount that can be produced per day decreases, resulting in a significant drop in CPE productivity.

Example Comparative example 2-1 2-2 2-1 2-2 2-3 Chlorination productivity 110% 110% 100% 65% 90%

As shown in Table 2, compared to the Comparative Example, the Examples have a small degree of CPE particle morphology deformation during the chlorination process due to the excellent thermal stability of polyethylene, thereby shortening the post-process time including drying time, which can be achieved by reducing the chlorination time per hour. It was confirmed that productivity could be improved.

Claims (14)

The melt index (MI ₅ ) measured at 190°C and 5 kg load by the method of ASTM D 1238 is 0.1 g/10min to 0.4 g/10min,
The molecular weight distribution (Mw/Mn) is 3 to 4.7,
The weight average molecular weight is 195000 g/mol to 230000 g/mol,
Polyethylene having a Thermal Stability Index (TSI) of the following formula 1 greater than 0 and less than or equal to 40:
[Equation 1]
TSI = (k1×M1) + (k2×M2) + (k3×M3) +k4
In equation 1,
M1 is the ratio (%) of the integral value in the area where Log Mw is 5.0 or more to less than 5.5 to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,
M2 is the ratio (%) of the integral value in the area where Log Mw is 5.5 or more to less than 6.0 to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,
M3 is the ratio (%) of the integral value of the area where Log Mw is 6.0 or more to the total integral value in the GPC curve graph of polyethylene where the x-axis is log Mw and the y-axis is dw/dlogMw,
k1 is 2.15 to 2.65, k2 is -6.95 to -5.65, k3 is -17.4 to -14.2, and k4 is 110.5 to 135.5.
According to paragraph 1,
The polyethylene is characterized in that it is an ethylene homopolymer.
polyethylene.
According to paragraph 1,
The polyethylene is characterized in that the density is 0.947 g/cm ³ to 0.954 g/cm ³ ,
polyethylene.
delete delete According to paragraph 1,
In Equation 1, k1 is 2.4, k2 is -6.33, k3 is -15.75, and k4 is 122.98.
polyethylene.
According to paragraph 1,
In Equation 1, M1 is 28 < M1 < 32, M2 is 16 < M2 < 18, and M3 is 2.5 < M3 < 3.6.
polyethylene.
At least one first metallocene compound represented by the following formula (1); and polymerizing ethylene by introducing hydrogen gas at 10 ppm to 35 ppm based on the ethylene content in the presence of a catalyst composition comprising at least one second metallocene compound selected from the compounds represented by the following formula (2). Including,
Method for producing polyethylene according to any one of claims 1 to 3, 6, and 7:
[Formula 1]
(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹ _3-n
In Formula 1,
M ¹ is Ti, Zr or Hf;
Cp ¹ and Cp ² are the same or different from each other, and are each independently selected from the group consisting of indenyl and 4,5,6,7-tetrahydro-1-indenyl radicals, and they are C1 to C20 hydrocarbons may be substituted;
R ^a and R ^b are the same or different from each other, and are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkoxyalkyl, or substituted or unsubstituted C7 to C40 is arylalkyl;
Z ¹ are the same as or different from each other and are each independently a halogen atom;
n is 1 or 0;
[Formula 2]

In Formula 2,
Q ¹ and Q ² are each independently of each other substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C2 to C20 alkoxyalkyl;
A is carbon, germanium, or silicon;
M ² is Ti, Zr or Hf;
X ¹ and X ² are the same as or different from each other and are each independently a halogen atom;
R ¹ to R ¹⁷ are the same or different from each other, and are each independently hydrogen, a halogen atom, substituted or unsubstituted C1 to C20 alkyl, or represented by the following formula (3),
However, at least one of R ² and R ⁷ is represented by the following formula (3), and at least one of R ¹⁰ and R ¹⁶ is represented by the following formula (3),
[Formula 3]
-L ¹ -D ¹
In Formula 3 above,
L ¹ is C1 to C10 alkylene,
D ¹ is C6 to C20 aryl, or C4 to C20 cycloalkyl.
delete According to clause 8,
The first metallocene compound is bis(3-(6-(tert-butoxy)hexyl)-1H-inden-1-yl)zirconium(IV) chloride, or bis(3-(6-(tert- Butoxy)hexyl)-4,5,6,7-tetrahydro-1H-inden-1-yl)zirconium(IV) chloride,
Method for producing polyethylene.
delete In Article 8,
The second metallocene compound is characterized in that it is dichloro[[[6-(tert-butoxy)hexyl]methylsilylene]bis[(4a,4b,8a,9,9a-η)-2-(cyclopentylmethyl)-9H-fluoren-9-ylidene]]zirconium, dichloro[[[6-(tert-butoxy)hexyl]methylsilylene]bis[(4a,4b,8a,9,9a-η)-2-(phenylmethyl)-9H-fluoren-9-ylidene]]zirconium, or dichloro[[[6-(tert-butoxy)hexyl]methylsilylene]bis[(4a,4b,8a,9,9a-η)-2-(cyclohexylmethyl)-9H-fluoren-9-ylidene]]zirconium.
Method for producing polyethylene.
According to clause 8,
The polymerization step is characterized in that it is performed under the conditions of a temperature of 80 ℃ to 84 ℃ and a pressure of 7.0 kg/cm ² to 9.0 kg/cm ² ,
Method for producing polyethylene.
Chlorinated polyethylene, produced by reacting the polyethylene of any one of claims 1 to 3, 6, and 7 with chlorine.