KR20210153556A - Polyethylene and its chlorinated polyethylene - Google Patents

Abstract

Polyethylene according to the present invention optimizes a high crystalline region in a molecular structure and reacting the same with chlorine so that chlorinated polyethylene having excellent processability and size stability during high-speed extrusion and a CPE compound including the same can be prepared.

Description

Polyethylene and its chlorinated polyethylene

The present invention relates to a polyethylene and a chlorinated polyethylene thereof, capable of producing a chlorinated polyethylene having excellent processability and size stability during high-speed extrusion by optimizing a high crystal region in a molecular structure.

Chlorinated polyethylene, produced by reacting polyethylene with chlorine, is known to have improved physical and mechanical properties compared to polyethylene, and can withstand particularly harsh external environments, so it is used as a packing material such as various containers, fibers, pipes, and heat transfer materials. used

Chlorinated polyethylene such as CPE (Chlorinated Polyethylene) is widely used for wires and cables through compounding with inorganic additives and crosslinking agents. In general, it is produced by reacting polyethylene with chlorine in a suspension state, or by reacting polyethylene with chlorine in aqueous HCl solution. It can be prepared by reacting with In the case of these CPE compound products, excellent tensile strength is required, and the strength of the compound varies according to the physical properties of the chlorinated polyethylene. In the case of general-purpose chlorinated polyethylene, which is widely known at present, since polyethylene using a Ziegler-Natta catalyst is applied, the molecular weight distribution is wide, and thus, there is a disadvantage in that the tensile strength is insufficient when manufacturing the CPE compound. When a metallocene catalyst is applied, processability may be insufficient because molecular weight distribution is generally narrow, but processability is improved by lowering CPE hardness due to excellent chlorine distribution uniformity.

However, when processing products such as thin wires and cables, because they undergo a high-speed extrusion process, polyethylene and chlorine react to minimize processing load so that excellent extrusion processability and extrusion size stability can be improved even during high-speed extrusion. The method has been continuously studied.

Accordingly, in order to significantly improve extrusion processability and size stability even during high-speed extrusion, excellent chlorine distribution uniformity is required in chlorinated polyethylene. This is constantly being demanded.

An object of the present invention is to provide polyethylene and chlorinated polyethylene thereof, capable of producing chlorinated polyethylene having excellent processability and size stability during high-speed extrusion by optimizing the high crystal region in the molecular structure.

In addition, the present invention is to provide a method for producing the polyethylene.

According to one embodiment of the invention, the MI ₅ ( ^{melt index measured at 190 o} C, 5 kg load) is 0.8 g/10 min to 1.4 g/10 min, and the melt flow index (MFRR _21.6/5 , method of ASTM D 1238) (The ^{value obtained by dividing the melt index measured at 190 o} C and 21.6 kg load by the melt index measured at 190 ^o C and 5 kg load) is 18 to 22, and on the temperature rise elution fractionation (TREF) graph, the elution temperature is 105 ^o A polyethylene is provided in which the ratio of the highly crystalline region showing a percentage value obtained by dividing the graph area of the high crystalline region corresponding to C or more by the total graph area is 10% or less.

In addition, the present invention provides a method for producing the polyethylene.

In addition, the present invention provides a chlorinated polyethylene prepared by reacting the polyethylene with chlorine.

The polyethylene according to the present invention can produce chlorinated polyethylene having excellent processability and size stability during high-speed extrusion by optimizing the high crystal region in the molecular structure and reacting it with chlorine.

1 shows a temperature rise elution fractionation (TREF) graph for the polyethylene of Example 1-1 and the polyethylene of Comparative Example 1-1 according to an embodiment of the present invention.

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 other components.

In addition, the terminology used herein is used only to describe exemplary embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as "comprise", "comprising" or "have" are intended to designate the existence of an embodied feature, number, step, element, or a combination thereof, but one or more other features or It should be understood that the existence or addition of numbers, steps, elements, or combinations thereof, is not precluded in advance.

In addition, the terms "about," "substantially," and the like, to the extent used throughout this specification are used in or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and are used in the meaning of the present application. It is used to prevent an unscrupulous infringer from using the disclosure in which exact or absolute figures are mentioned for better understanding.

In addition, in the present specification, "part by weight" means a relative concept in which the weight of the other material is expressed as a ratio based on the weight of a certain material. For example, in a mixture in which the weight of material A is 50 g, the weight of material B is 20 g, and the weight of material C is 30 g, based on 100 parts by weight of material A, the amounts of material B and material C are each 40 parts by weight and 60 parts by weight.

In addition, "% by weight (% by weight)" means an absolute concept in which the weight of a certain material is expressed as a percentage of the total weight. In the mixture exemplified above, the content of material A, material B, and material C in 100% of the total weight of the mixture is 50% by weight, 20% by weight, and 30% by weight, respectively. At this time, the sum of the contents of each component does not exceed 100% by weight.

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

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

According to one embodiment of the present invention, there is provided a polyethylene capable of producing chlorinated polyethylene having excellent processability and size stability during high-speed extrusion by implementing a molecular structure in which a high crystal region is optimized.

The polyethylene has a MI ₅ ( ^{melt index measured at 190 o} C, 5 kg load) of 0.8 g/10min to 1.4 g/10min, and a melt flow index (MFRR _21.6/5 ^{, ASTM D 1238 at 190 o} C by the method of D 1238). , the melt index measured at 21.6 kg load ^{divided by the melt index measured at 190 o} C and 5 kg load) is 18 to 22, and on the temperature rise elution fractionation (TREF) graph, it corresponds to the ^{elution temperature of 105 o C or higher} It is characterized in that the ratio of the highly crystalline region representing a percentage value obtained by dividing the graph area of the highly crystalline region by the total graph area is 10% or less.

The polyethylene according to the present invention can provide chlorinated polyethylene having excellent processability and size stability during high-speed extrusion by optimizing the high crystal region in the molecular structure.

In particular, in the polyethylene of the present invention, the high crystal region in the molecular structure is reduced, so that the residual crystallinity of the chlorinated polyethylene is lowered under the same chlorination condition. As such, the lower the residual crystals of chlorinated polyethylene, the lower the hardness, and the better dispersibility in the chlorinated polyethylene compound using the same, the processability shown in the pattern viscosity and size stability shown in the plasticity can be significantly improved.

The polyethylene according to the present invention may be an ethylene homopolymer that does not include a separate copolymer.

The polyethylene is prepared by optimizing a specific metallocene catalyst, as will be described later, so that MI ₅ ( ^{melt index measured at 190 o} C, 5 kg load) and melt flow index (MFRR _21.6/5 , ASTM D 1238) method (the ^{value obtained by optimizing the melt index measured at 190 o} C and 21.6 kg load by the melt index measured at 190 ^o C and 5 kg load), and at the same time, By optimizing the ratio, chlorinated polyethylene with excellent processability and size stability during high-speed extrusion can be provided, and the tensile strength and plasticity of CPE compound can be improved.

_{The polyethylene, as described above, has a melt index MI 5} of about 0.8 g/10min to about 1.4 g/10min, measured by the method of ASTM D 1238 at a temperature of 190 ^o C and a load of 5 kg. The melt index MI ₅ should be about 1.4 g/10min or less in terms of securing excellent thermal stability because the lower the MI, the higher the viscosity, so the polyethylene particle shape change is small in a high-temperature slurry state for chlorination. However, in a more preferred range, the melt index MI ₅ is about 1.39 g/10min or less, or about 1.38 g/10min or less, or about 1.36 g/10min or less, or about 1.35 g/10min or less, or about 1.34 g/10min or less or less, or about 1.32 g/10min or less, or about 1.3 g/10min or less. In addition, the melt index MI ₅ should be 0.8 g/10min or more in terms of securing excellent processability as the viscosity decreases as the MI increases. Specifically, the melt index MI ₅ is about 0.85 g/10min or more, or about 0.9 g/10min or more, or about 0.95 g/10min or more, or about 1.0 g/10min or more, or about 1.05 g/10min or more, or about 1.1 g/10 min or more. In particular, the polyethylene of the present invention secures excellent extrusion processability and size stability even in a high-speed extrusion process when applied to electric wires and cables, and at the same time enables excellent mechanical properties such as tensile strength. It is preferred to have a melt index MI _{5 in the range.}

In addition, the polyethylene has a melt flow index (MFRR _21.6/5 , the melt index measured at ^{190 o} C, 21.6 kg load by the method of ASTM D 1238 divided by the melt index measured at ^{190 o C, 5 kg load)} is from about 18 to about 22. Specifically, the melt flow index can be from about 18 to about 21.5, or from about 18 to about 21, or from about 18.5 to about 21, or from about 19 to about 21, or from about 19 to about 20.5, or from about 19 to about 20 have. The melt flow index should be about 18 or more in terms of processability during extrusion, and should be about 22 or less in terms of securing excellent mechanical properties by increasing the Mooney viscosity (MV) of CPE.

The melt flow index (MFRR _21.6/5 ) is a value obtained by dividing the melt index measured at ^{190 °} C and 21.6 kg load by the method of ASTM D 1238 by the melt index measured at 190 ^{°C, 5 kg load.} _{Here, the melt index MI 21.6} measured by the method of ASTM D 1238 ^{under the conditions of a temperature of 190 °} C and a load of 21.6 kg is about 20 g/10 min to about 30 g/10 min, or about 21 g/10 min to about 28 g/10 min, or from about 22 g/10 min to about 26 g/10 min.

_{In addition, the polyethylene may have a melt index MI of 2.16} ^{measured at a temperature of 190 o} C and a load of 2.16 kg by the method of ASTM D 1238 of about 0.01 g/10 min to about 0.45 g/10 min. The melt index MI _2.16 may be about 0.45 g/10min or less in terms of securing excellent thermal stability as described above. In a more preferred range, the melt index MI _2.16 may be about 0.44 g/10min or less, about 0.43 g/10min or less, about 0.42 g/10min or less, about 0.41 g/10min or less, or about 0.40 g/10min or less. In addition, the melt index MI _2.16 may be 0.01 g/10min or more in terms of securing excellent processability as described above. Specifically, the melt index MI _2.16 is about 0.02 g/10min or more, or about 0.05 g/10min or more, or about 0.1 g/10min or more, or about 0.15 g/10min or more, or about 0.18 g/10min or more, or about at least 0.2 g/10min, or at least about 0.22 g/10min, or at least about 0.24 g/10min, or at least about 0.26 g/10min, or at least about 0.28 g/10min. In particular, the polyethylene of the present invention secures excellent extrusion processability and size stability even in a high-speed extrusion process when applied to electric wires and cables, and at the same time enables excellent mechanical properties such as tensile strength. It is preferred to have a melt index MI of _{2.16 in the range.}

On the other hand, the polyethylene of the present invention is characterized in that the ratio of the high crystalline region on the temperature rise elution fractionation (TREF) graph is small _{with the melt index MI 5} and the melt flow index (MFRR _{21.6/5) optimized as described above.} .

The polyethylene, on the temperature rise elution fractionation (TREF) graph, the ratio of the high crystal region is about 10% or less, or about 3% to about 10% appears as small. Specifically, the proportion of the highly crystalline region is about 9.5% or less, or about 3% to about 9.5%, or about 9% or less, or about 3.5% to about 9%, or about 8.5% or less, or about 4% to about 8.5% , or about 8.0% or less, or about 5% to about 8.0%, or about 7.8% or less, or about 5.5% to about 7.8%. Specifically, the lower the ratio of the high-crystal region, the easier the chlorine molecules to penetrate into the crystal, so that it should be about 10% or less in terms of a uniform chlorination reaction. However, when the ratio of the high crystalline region is excessively low, the crystal arrangement easily occurs, the chlorination productivity may decrease, and the strength may be insufficient. have.

The ratio of the highly crystalline region may be obtained from a temperature rise elution fractionation (TREF) graph for polyethylene, as exemplified in one embodiment of FIG. 1 . First, after obtaining a temperature rising elution fractionation (TREF) graph of the polyethylene, on the basis of the elution temperature of 105 ^o C a high-determining region on the TREF graph, the elution to the elution temperature of temperature 105 ^o C point basis, with the vertical axis A region with a temperature of 105 ^o C or higher is called a highly crystalline region. From this, the graph area of the high crystalline region corresponding to the elution temperature or higher of the minimum value is measured, and a percentage value obtained by dividing the graph area by the total graph area is expressed as the high crystalline region ratio (%).

Specifically, a temperature rise elution fractionation (TREF) graph of polyethylene can be obtained through an Agilent Technologies 7890A instrument from PolymerChar. For example, after dissolving a sample at a concentration of 1.5 mg/mL in 20 mL of 1,2,4-trichlorobenzene, and then dissolving by increasing the temperature from ^{30 o} C to 150 ^o C at ^{a rate of 40 o C/min} , the graph can be obtained through the process of recrystallization by lowering the temperature to ^{35 o} C at ^{a rate of 0.5 o} C/min, and elution while raising the temperature at a rate of 1 ^{o C/min to 140 o C again.}

The temperature rise elution fractionation (TREF) graph of polyethylene thus obtained, as exemplified in one embodiment of FIG. 1 , shows the elution temperature ( ^o C) on the X-axis, and the amount of elution at that temperature on the Y-axis (dW/ dt). The area occupied by the graph corresponding to the temperature equal to or higher than ^{the elution temperature of 105 o} C on the temperature rise elution fractionation (TREF) graph is called a highly crystalline region. That is, the value obtained by integrating the area of the graph corresponding to the temperature higher than the elution temperature of 105 ^o C as the vertical axis can be referred to as the area of the highly crystalline region. A percentage value obtained by dividing the area of the highly crystalline region by the total graph area may be referred to as a ratio of the highly crystalline region.

On the other hand, the density of the polyethylene is about 0.955 g/cm ³ to about 0.960 g/cm ³ , or about 0.9565 g/cm ³ to about 0.9595 g/cm ³ , or about 0.956 g/cm ³ to about 0.959 g/cm ³ can be In particular, the density of the polyethylene is about 0.955 g/cm ³ or more, which means that the content of the crystal structure of polyethylene is high and dense, and thus it is difficult to change the crystal structure during the chlorination process. However, when the density of the above-mentioned polyethylene ^{exceeds about 0.960 g/cm 3} , the content of the crystal structure of the polyethylene becomes too large, and the area of the TREF high crystallinity region increases, so that the heat of fusion increases during CPE processing. Machinability may decrease. Accordingly, the polyethylene of the present invention secures excellent extrusion processability and size stability even in a high-speed extrusion process when applied to electric wires and cables, and in terms of exhibiting excellent mechanical properties such as tensile strength, It is desirable to have a density in the range.

The polyethylene according to the present invention has a molecular weight distribution of from about 2 to about 10, or from about 4 to about 10, or from about 5 to about 9, or from about 6.5 to about 8.2, or from about 7.0 to about 8.0, or from about 7.2 to about 7.6 can be In particular, since the polyethylene of the present invention has the molecular weight distribution as described above, it is possible to obtain a product having a CPE MV of 50 to 60 and excellent processability.

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

Specifically, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyethylene can be measured using a polystyrene calibration curve. For example, as a gel permeation chromatography (GPC) apparatus, a Waters PL-GPC220 instrument may be used, and a Polymer Laboratories PLgel MIX-B 300 mm long column may be used. At this time, the measurement temperature is 160 ^o C, 1,2,4-trichlorobenzene can be used as a solvent, and the flow rate can be applied at 1 mL/min. Each polyethylene sample was pretreated by dissolving it in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% of BHT at 160 ^° C for 10 hours using a GPC analysis device (PL-GP220), and 10 mg/10 mL of It can be formulated to a concentration and then supplied in an amount of 200 microliters (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 the polystyrene standard specimen is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 400000 g/mol, 1000000 g Nine types of /mol can be used.

The polyethylene may have a weight average molecular weight of about 110000 to about 250000 g/mol. Preferably, the weight average molecular weight of the polyethylene is at least about 120000 g/mol, or at least about 125000 g/mol, or at least about 130000 g/mol, or at least about 1350000 g/mol, or at least about 140000 g/mol; or at least about 145000 g/mol, or at least about 147000 g/mol. Further, the weight average molecular weight of the polyethylene is about 220000 g/mol or less, or about 200000 g/mol or less, or about 180000 g/mol or less, or about 170000 g/mol or less, or about 160000 g/mol or less, or about 155000 g/mol or less, or about 153000 g/mol or less. It shows an appropriate molecular weight so that CPE MV 50 to 60 can be obtained and strength is excellent.

In particular, when the weight average molecular weight of the polyethylene is too low, chlorination productivity may be reduced in the chlorination process, and the weight average molecular weight of the polyethylene may be about 110000 g/mol or more. However, when the weight average molecular weight of the polyethylene is too high, processability may be reduced, and the weight average molecular weight of the polyethylene may be about 250000 g/mol or less. The polyethylene of the present invention has excellent chlorination productivity when applied to electric wires and cables, and preferably has a weight average molecular weight within the above-described range in terms of realizing balanced properties of MV, processability, tensile strength, and plasticity. .

On the other hand, according to another embodiment of the invention, there is provided a method for producing the polyethylene as described above.

The method for producing polyethylene according to the present invention includes at least one first metallocene compound represented by the following Chemical Formula 1; and polymerizing ethylene in the presence of at least one second metallocene compound selected from compounds represented by the following Chemical Formula 2, wherein the weight ratio of the first metallocene compound and the second metallocene compound is 40:60 to 45:55.

[Formula 1]

In Formula 1,

Any one or more of R ₁ to R _{8 is -(CH 2} ) _n -OR, wherein R is C _1-6 straight or branched chain alkyl, n is an integer from 2 to 6,

The _{rest of R 1} to R ₈ are the same as or different from each other and are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-40 alkylaryl, C _{7- 40 It} is a functional group selected from the group consisting of arylalkyl, or two or more adjacent to each other are connected to each other to form a C _6-20 aliphatic or aromatic ring _{unsubstituted or substituted with a C 1-10 hydrocarbyl group,} ,

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

A ₁ is carbon (C), silicon (Si), or germanium (Ge);

M ₁ is a Group 4 transition metal;

X ₁ and X ₂ are the same as or different from each other, and each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, nitro group, amido group, C _1-20 alkylsilyl, C _1-20 alkoxy, or C _1-20 sulfonate group;

m is an integer of 0 or 1,

[Formula 2]

In Formula 2,

Q ₃ and Q ₄ are the same as or different from each other, and each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkoxyalkyl, C _6-20 aryl, C _7-40 alkyl aryl, C _7-40 arylalkyl;

A ₂ is carbon (C), silicon (Si), or germanium (Ge);

M ₂ is a Group 4 transition metal;

X ₃ and X ₄ are the same as or different from each other, and each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, nitro group, amido group, C _1-20 alkylsilyl, C _1-20 alkoxy, or C _1-20 sulfonate group;

C ₁ and C ₂ is one of which is represented by Formula 3a or Formula 3b, C ₁ and The _{other one of C 2} is represented by Formula 3c, Formula 3d, or Formula 3e;

[Formula 3a]

[Formula 3b]

[Formula 3c]

[Formula 3d]

[Formula 3e]

In Formulas 3a, 3b, 3c, 3d and 3e, R ₉ to R ₂₁ and R _17' to R _21' are the same as or different from each other, and each independently hydrogen, halogen, C _1-20 alkyl, C _1-20 Haloalkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 arylalkyl, provided that at least one of _{R 17} to R ₂₁ and R _17′ to R _{21′ is C 1-20} haloalkyl;

R ₂₂ to R ₃₉ are the same as or different from each other, and each independently hydrogen, halogen, C _1-20 alkyl, C _1-20 haloalkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 arylalkyl, or two adjacent _{R 22} to R ₃₉ or more may be connected to each other to form a C _6-20 aliphatic or aromatic ring _{substituted or unsubstituted with a C 1-10 hydrocarbyl group;}

* indicates a site binding to _{A 2} and M _{2 .}

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

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

The hydrocarbyl group is a monovalent functional group in which a hydrogen atom is removed from hydrocarbon, and is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenylaryl group, and an alkyl group. It may include a nylaryl group and the like. The hydrocarbyl group having 1 to 30 carbon atoms may be a hydrocarbyl group having 1 to 20 carbon atoms or 1 to 10 carbon atoms. For example, the hydrocarbyl group may be a straight chain, branched chain or cyclic alkyl group. More specifically, the hydrocarbyl group having 1 to 30 carbon atoms is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, and a n-hexyl group. straight-chain, branched-chain or cyclic alkyl groups such as a sil group, n-heptyl group, and cyclohexyl group; or an aryl group such as phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, or fluorenyl. In addition, it may be an alkylaryl such as methylphenyl, ethylphenyl, methylbiphenyl, or methylnaphthyl, and may be an arylalkyl such as phenylmethyl, phenylethyl, biphenylmethyl, or naphthylmethyl. In addition, it may be an alkenyl such as allyl, allyl, ethenyl, propenyl, butenyl, pentenyl.

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

The alkenyl having 2 to 20 carbon atoms (C _2-20 ) includes straight-chain or branched alkenyl, and specifically includes allyl, allyl, ethenyl, propenyl, butenyl, pentenyl, and the like. but is not limited.

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

The alkoxyalkyl group having 2 to 20 (C _2-20 ) is a functional group in which one or more hydrogens of the aforementioned alkyl are substituted with alkoxy, specifically methoxymethyl, methoxyethyl, ethoxymethyl, iso-propoxymethyl, alkoxyalkyl such as iso-propoxyethyl, iso-propoxypropyl, iso-propoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxypropyl, and tert-butoxyhexyl; The present invention is not limited thereto.

The aryloxy having 6 to 40 carbon atoms (C _6-40 ) may include, but is not limited to, phenoxy, biphenoxyl, and naphthoxy.

The aryloxyalkyl group having 7 to 40 carbon atoms (C _7-40 ) is a functional group in which one or more hydrogens of the aforementioned alkyl are substituted with aryloxy, and specifically, phenoxymethyl, phenoxyethyl, phenoxyhexyl, etc. may be mentioned. , but is not limited thereto.

Alkylsilyl having 1 to 20 (C _1-20 ) or an alkoxysilyl group having 1 to 20 (C _1-20 ) is -SiH ₃ 1 to 3 hydrogens are 1 to 3 alkyl or alkoxy as described above. A substituted functional group, specifically, alkylsilyl, such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl group or dimethylpropylsilyl; alkoxysilyl such as methoxysilyl, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl; alkoxyalkylsilyl such as methoxydimethylsilyl, diethoxymethylsilyl, or dimethoxypropylsilyl, but is not limited thereto.

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

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

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

_Alkylaryl having 7 to 20 carbon atoms (C 7-20 ) may refer to a substituent in which one or more hydrogens among hydrogens of an aromatic ring are substituted by the aforementioned alkyl. For example, the alkylaryl having 7 to 20 carbon atoms (C _7-20 ) may include, but is not limited to, methylphenyl, ethylphenyl, methylbiphenyl, methylnaphthyl, and the like.

The arylalkyl having 7 to 20 carbon atoms (C _7-20 ) may mean a substituent in which one or more hydrogens of the aforementioned alkyl are substituted by the aforementioned aryl. For example, the arylalkyl having 7 to 20 carbon atoms (C _7-20 ) may include, but is not limited to, phenylmethyl, phenylethyl, biphenylmethyl, naphthylmethyl, and the like.

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

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

In addition, the group 13 element may be boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), specifically, boron (B), or aluminum (Al). and is not limited thereto.

Meanwhile, the first metallocene compound may be represented by any one of the following Chemical Formulas 1-1 to 1-4.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4, Q ₁ , Q ₂ , A ₁ , M ₁ , X ₁ , X ₂ , and R ₁ to R ₈ are as defined in Formula 1, and R′ and R′′ are the same as or different from each other and each independently represent a C _1-10 hydrocarbyl group.

Preferably, the first metallocene compound may have a structure including a bis-cyclopentadienyl ligand, and more preferably, a cyclopentidienyl ligand configured symmetrically with respect to a transition metal. More preferably, the first metallocene compound may be represented by Formula 1-1.

In Formulas 1 and 1-1 to 1-4, any one or more of _{R 1} to R _{8 is -(CH 2} ) _n -OR, where R is C _1-6 straight-chain or branched alkyl; , n is an integer from 2 to 6. Specifically, R is C _1-4 straight or branched chain alkyl, and n is an integer of 4 to 6. For example, any one or more of _{R 1} to R _{8 may be C 2-6} alkyl substituted with C _1-6 alkoxy, or _{C 4-6} alkyl substituted with C _{1-4 alkoxy.}

In Formulas 1 and 1-1 to 1-4, the _{rest of R 1} to R ₈ are the same as or different from each other and are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _{6 -20} aryl, C _7-40 alkylaryl, C _{7-40 a} functional group selected from the group consisting of arylalkyl, or two or more adjacent to each other are connected to each other and substituted or unsubstituted _{with a C 1-10 hydrocarbyl group} It may form a C _6-20 aliphatic or aromatic ring.

Specifically, the _{rest of R 1} to R ₈ are each hydrogen, or C _1-20 alkyl, or C _1-10 alkyl, or C _1-6 alkyl, or _{C 2-6} alkyl substituted with C _{1-6 alkoxy.} , or C _1-4 alkoxy may be substituted C _4-6 alkyl. Alternatively, two or more adjacent to each other among _{R 1} to R ₈ may be connected to each other to form a C _6-20 aliphatic or aromatic ring _{substituted with C 1-3.}

Preferably, in Formulas 1 and 1-1 to 1-4, R ₃ and R ₆ are each C _1-6 alkyl or _{C 2-6} alkyl substituted with C _1-6 alkoxy, provided that At least one of R ₃ and R _{6 is C 2-6} alkyl substituted with C _{1-6 alkoxy.} Or, wherein R ₃ and R ₆ is C _4-6 alkyl, or C _1-4 alkoxy which may be substituted with C _4-6 alkyl, with the proviso that the R ₃ and R ₆ at least one of each is C _{1- 4} alkoxy is substituted C _4-6 alkyl. For example, R ₃ and R ₆ may each be n-butyl, n-pentyl, n-hexyl, tert-butoxy butyl, or tert-butoxy hexyl, with the proviso that at least one of _{R 3} and R ₆ above is ert-butoxy butyl, or tert-butoxy hexyl. Preferably, R ₃ and R ₆ are the same as each other, and may be tert-butoxy butyl or tert-butoxy hexyl.

And, in Formulas 1 and 1-1 to 1-4, R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , and R ₈ may be hydrogen.

In Formulas 1 and 1-2, and Formula 1-4, Q ₁ and Q ₂ are the same as or different from each other, and each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _{2- 20} alkoxyalkyl, C _6-20 aryl, C _7-40 alkylaryl, C _7-40 arylalkyl.

Specifically, Q ₁ and Q ₂ may each be C _1-12 alkyl, C _1-6 alkyl, or C _1-3 alkyl. Preferably, Q ₁ and Q ₂ are the same as each other, and may be _{C 1-3 alkyl.} More preferably, Q ₁ and Q ₂ may be methyl.

In Chemical Formulas 1 and 1-1 to 1-4, A ₁ is carbon (C), silicon (Si), or germanium (Ge). Specifically, A ₁ may be silicon (Si).

In Chemical Formulas 1 and 1-1 to 1-4, M ₁ is a Group 4 transition metal. Specifically, M ₁ may be zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).

In Formulas 1 and 1-1 to 1-4, X ₁ and X ₂ are the same as or different from each other, and each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl; nitro group, amido group, C _1-20 alkylsilyl, C _1-20 alkoxy, or C _1-20 sulfonate group. Specifically, X ₁ and X ₂ may each be halogen, and each may be chloro, iodine, or bromine. Preferably, the X ₁ and X ₂ may be chloro.

In Formula 1, m is 0 or an integer of 1, and preferably m is 0.

The compound represented by Formula 1 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

Preferably, the first metallocene compound may be a compound represented by one of the following structural formulas.

.

.

More preferably, the first metallocene compound may be a compound represented by one of the following structural formulas.

.

.

The first metallocene compound represented by the above structural formulas may be synthesized by applying known reactions, and for a more detailed synthesis method, refer to Examples.

In the method for producing polyethylene according to the present invention, at least one first metallocene compound represented by Chemical Formula 1 or Chemical Formulas 1-1, 1-2, 1-3, and 1-4 as described above, which will be described later By using it together with one or more second metallocene compounds, the melt index MI ₅ and the melt flow index (MFRR _21.6/5 ) of polyethylene are optimized, and at the same time, the high crystalline region according to the temperature rise elution fractionation (TREF) analysis. By optimizing the ratio, excellent extrusion processability and size stability are realized even during high-speed extrusion in the CPE process to be described later, and at the same time, it is possible to improve the tensile strength and plasticity of the CPE compound with high productivity.

Meanwhile, the second metallocene compound may be represented by the following Chemical Formula 2-1.

[Formula 2-1]

In Formula 2-1, Q ₃ , Q ₄ , A ₂ , M ₂ , X ₃ , X ₂₄ , R ₁₁ , and R ₁₇ to R ₂₉ are as defined in Formula 2 above.

In Formulas 2 and 2-1, Q ₃ and Q ₄ are the same as or different from each other, and each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkoxyalkyl, C _{6 -20} aryl, C _7-40 alkylaryl, C _7-40 arylalkyl. Specifically, Q ₃ and Q ₄ are each C _1-12 alkyl, or C _1-8 alkyl, or C _1-3 alkyl, or C _2-18 alkoxyalkyl, or C _2-14 alkoxyalkyl, or C _{2 It} may be -12 alkoxyalkyl, and more specifically, Q ₃ and Q ₄ may each be C _1-3 alkyl, or C _2-12 alkoxyalkyl. Preferably, Q ₃ and Q ₄ are different from each other, _{and one of Q 3} and Q ₄ may be C _1-3 alkyl, and the other may be C _2-12 alkoxyalkyl. More preferably _{, one of Q 3} and Q ₄ may be methyl, and the other may be tert-butoxyhexyl.

In Formulas 2 and 2-1, A ₂ is carbon (C), silicon (Si), or germanium (Ge). Specifically, A ₂ may be silicon (Si),

In Formulas 2 and 2-1, M ₂ is a Group 4 transition metal. Specifically, M ₂ may be zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).

In Formulas 2 and 2-1, X ₃ and X ₄ are the same as or different from each other, and each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, nitro group, and amido group , C _1-20 alkylsilyl, C _1-20 alkoxy, or C _1-20 sulfonate group. Specifically, X ₃ and X ₄ may each be halogen, and each may be chloro, iodine, or bromine. Preferably, X ₃ and X ₄ may be chloro.

In Formula 2, C ₁ and One of C ₂ is represented by Formula 3a or Formula 3b, C ₁ and The _{other one of C 2} is represented by Formula 3c, Formula 3d, or Formula 3e, and preferably may be represented by Formula 3c.

In Formulas 2 and 2-1, R ₉ to R ₂₁ and R _17' to R _21' are the same as or different from each other, and each independently hydrogen, halogen, C _1-20 alkyl, C _1-20 haloalkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _6-20 aryl, C _7-40 alkylaryl, or C _{7- 40} arylalkyl, provided that at least one of _{R 17} to R ₂₁ and R _17′ to R _{21′ is C 1-20} haloalkyl.

Specifically, in Formula 2, R ₉ to R ₁₀ and R ₁₂ to R ₁₆ and R _9′ to R _10′ and R _12′ to R _16′ may be hydrogen.

Specifically, in Formulas 2 and 2-1, R ₁₁ and R _11' may each be a C _1-6 straight-chain or branched chain alkyl, or C _1-3 straight-chain or branched chain alkyl, Preferably, it may be methyl.

Specifically, in Formulas 2 and 2-1, R ₁₇ to R ₂₁ and R _17' to R _21' may each be hydrogen or C _1-6 haloalkyl, provided that R ₁₇ to R ₂₁ and R At least one of _17' to R _{21' is C 1-6} haloalkyl. Alternatively, R ₁₇ to R ₂₁ and R _17′ to R _21′ may each be hydrogen or C _1-3 haloalkyl, provided that at least one of _{R 17} to R ₂₁ and R _17′ to R _{21′ is} C _1-3 haloalkyl. For example, R ₁₇ to R ₂₀ or R _17′ to R _20′ are hydrogen, and R ₂₁ or R _21′ is trihalomethyl, preferably trifluoromethyl.

In Formulas 2 and 2-1, R ₂₂ to R ₃₉ are the same as or different from each other, and each independently hydrogen, halogen, C _1-20 alkyl, C _1-20 haloalkyl, C _2-20 alkenyl, C _{1 -20} alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 arylalkyl, or R Two or more adjacent to each other of ₂₂ to R ₃₉ may be connected to each other to form a C _6-20 aliphatic or aromatic ring _{unsubstituted or substituted with a C 1-10 hydrocarbyl group.}

Specifically, each of R ₂₂ to R ₂₉ may be hydrogen, or C _1-20 alkyl, or C _1-10 alkyl, or C _1-6 alkyl, or C _1-3 alkyl. Alternatively, two or more adjacent to each other among _{R 22} to R ₂₉ may be connected to each other to form a C _6-20 aliphatic or aromatic ring _{substituted with C 1-3 .} Preferably, R ₂₂ to R ₂₉ may be hydrogen.

In Formulas 2 and 2-1,

Specifically, R ₃₀ to R ₃₅ may each be hydrogen, or C _1-20 alkyl, or C _1-10 alkyl, or C _1-6 alkyl, or C _1-3 alkyl.

In Formulas 2 and 2-1,

Specifically, each of R ₂₆ to R ₂₉ may be hydrogen, or C _1-20 alkyl, or C _1-10 alkyl, or C _1-6 alkyl, or C _1-3 alkyl.

The compound represented by Formula 2 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

The second metallocene compound represented by the above structural formula may be synthesized by applying known reactions, and more detailed synthesis methods may refer to Examples.

The method for preparing the metallocene compound was specifically described in Examples to be described later.

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

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

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

Specifically, the cocatalyst may be at least one selected from the group consisting of compounds represented by the following Chemical Formulas 4 to 6:

[Formula 4]

-[Al(R ₄₀ )-O] _c -

In Formula 4,

R ₄₀ 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 ₄₁ ) ₃

In Formula 5,

D is aluminum or boron,

R ₄₁ is each independently hydrogen, halogen, C _1-20 hydrocarbyl or halogen-substituted C _1-20 hydrocarbyl;

[Formula 6]

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

In Formula 6,

L is a neutral or cationic Lewis base,

[LH] ⁺ is a Bronsted acid,

Q is Br ³⁺ or Al ³⁺ ,

E is each independently C _6-20 aryl or C _1-20 alkyl, wherein said C _6-20 aryl or C _1-20 alkyl is unsubstituted or 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, alkylaluminoxane such as modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like.

The alkyl metal compound represented by the formula (5) is, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethylchloro Aluminum, triisopropylaluminum, tri-t-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolyl aluminum, dimethylaluminummethoxide, dimethylaluminumethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like.

The compound represented by the formula (6) is, for example, triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, 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 tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenyl boron, N, N-diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetra Phenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium 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 tetraphenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluoro Rophenylaluminum, diethylammonium tetrapentafluorophenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, triphenylcarboniumtetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenyl Carbonium tetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetrapentafluorophenylboron, etc. may be used.

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

In the supported metallocene catalyst according to the present invention, as the carrier, a carrier containing a hydroxyl group on the surface may be used, and it is preferably dried to remove moisture from the surface and has a highly reactive hydroxyl group and a siloxane group. carrier can be used.

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

The drying temperature of the carrier ^{is preferably from about 200 o} C to about 800 ^o C, more preferably from about 300 ^o C to about 600 ^o C, and most preferably from ^{about 300 o} C to 400 ^{o C.} When the drying temperature of the carrier is ^{less than about 200 o} C, there is too much moisture and the surface moisture and the cocatalyst react, and ^{when it exceeds about 800 o} C, the pores on the surface of the carrier are combined and the surface area is reduced, and also on the surface It is undesirable because many hydroxyl groups disappear and only siloxane groups remain, reducing the reaction site with the co-catalyst.

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

If the amount of the hydroxyl group is less than about 0.1 mmol/g, there are few reaction sites with the co-catalyst, and if it exceeds about 10 mmol/g, there is a possibility that it is due to moisture other than the hydroxyl group present on the surface of the carrier particle. Not desirable.

In the supported metallocene catalyst according to the present invention, the mass ratio of the total transition metal to the support included in the metallocene catalyst may be from about 1:10 to about 1:1000. When the carrier and the metallocene compound are included in the above mass ratio, an optimal shape may be exhibited. Also, the mass ratio of the promoter compound to the carrier may be from about 1:1 to about 1:100.

The ethylene polymerization reaction may be carried out using one 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 may include at least one first metallocene compound represented by Chemical 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 should be, for example, about 40:60 to about 45:55. Specifically, the weight ratio of the first and second metallocene compounds may be from about 41:59 to about 44:56, or from about 42:58 to about 43:57. The weight ratio of the catalyst precursor optimizes the high crystalline region in the molecular structure so that chlorinated polyethylene and CPE compounds with excellent size stability as well as high extrusion processability can be produced even during high-speed extrusion in the process of manufacturing wires or cables. The weight ratio should be as described above in terms of optimizing the highly crystalline region in the structure. Specifically, the weight ratio is, the ratio of the high crystal region of polyethylene is 10% or less, and when the melt index MI ₅ is 0.8 g/10min to 1.4 g/10min, MFRR (21.6/5) is 18 or more. It can be about 40:60 or more, and it can be about 45:55 or less in terms of MFRR (21.6/5) being optimized to 22 or less.

In addition, in the present invention, the polyethylene may be prepared while introducing hydrogen gas under the metallocene catalyst as described above. At this time, the hydrogen gas may be introduced in an amount of about 100 ppm to about 150 ppm, or about 110 ppm to about 140 ppm, or about 115 ppm to about 135 ppm, or about 120 ppm to about 130 ppm. The input amount of hydrogen gas may be maintained in the range as described above in terms of minimizing the intramolecular high crystal region while the _{polyethylene obtained after polymerization exhibits the melt index MI 5 and the melt flow index in the optimal range at the same time.} In particular, the polyethylene lowers the hardness by reducing the residual crystals of CPE under the same chlorination condition, and it is preferable in terms of improving processability (comp'd MV) and size stability (plasticity) with excellent dispersibility in the CPE compound The hydrogen gas may be introduced in an amount of about 115 ppm or more or about 120 ppm or more.

On the other hand, when hydrogen gas is added in excess of 150 ppm, the content of wax in the polymerization reaction solvent, for example, hexane increases, so that a problem in which particles agglomerate during the chlorination reaction may occur. In addition, in the polymerization process of the present invention, the wax content is maintained as low as 20% or less, and the amount of hydrogen input can be adjusted. The wax content can be measured as a volume ratio occupied by wax by separating the polymerization product by using a centrifugal separation device, sampling 100 mL of the remaining hexane solvent and settling for 2 hours.

And, the polymerization temperature may be about 25 ^o C to about 500 ^o C, preferably about 25 ^o C to about 200 ^o C, more preferably about 50 ^o C to about 150 ^o C. Further, the polymerization pressure is about 1 kgf/cm ² to about 100 kgf/cm ² , preferably about 1 kgf/cm ² to about 50 kgf/cm ² , more preferably about 5 kgf/cm ² to about 30 kgf It can be /cm ^{2 .}

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

On the other hand, according to another embodiment of the invention, there is provided a chlorinated polyethylene (CPE) using the polyethylene as described above.

The chlorinated polyethylene according to the present invention may be prepared by polymerizing ethylene in the presence of the above-described supported metallocene catalyst and then reacting it with chlorine.

In the reaction with chlorine, after dispersing the prepared polyethylene with water, an emulsifier and a dispersant, a catalyst and chlorine may be added to react.

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

The catalyst may use a chlorination catalyst used in the art, for example, benzoyl peroxide may be used. The chlorine may be used alone, but may be mixed with an inert gas.

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

The chlorinated polyethylene prepared by the above reaction may be additionally subjected to a neutralization process, a washing process, and/or a drying process, and thus may be obtained in the form of a powder.

On the other hand, as described above, the chlorinated polyethylene according to the present invention _{optimizes both the melt index MI5 and the melt flow index MFRR 21.6/5 of} polyethylene and the high crystalline region in the molecular structure together with a specific pattern viscosity and low hardness and By having heat of fusion, it is possible to improve all of the chlorination productivity in the chlorination process with MV, processability, tensile strength, and plasticity to an excellent degree when processing CPE compounds for applications such as wires and cables.

In particular, the chlorinated polyethylene exhibits excellent uniformity of chlorine distribution in chlorinated polyethylene because polyethylene has a narrow molecular weight distribution, for example, in a slurry (water or HCl aqueous solution) state of about 60 ^o C to about 150 ^o C. After preparing by reacting , the ^{MV (Mooney viscosity) measured under the condition of 121 o} C is from about 50 or more to about 60 or less. Specifically, the Mooney viscosity (MV) of the chlorinated polyethylene is about 50.5 or more, or about 51 or more, or about 51.5 or more, or about 52 or more, and up to about 59 or less, or about 58 or less, or about 57 up to, or up to about 56, or up to about 55, or up to about 54 or less. In particular, the chlorinated polyethylene may be mainly used for thin wires, and may exhibit the above-described pattern viscosity range in terms of securing size stability during high-speed extrusion. In addition, when the pattern viscosity of the chlorinated polyethylene is too high, as will be described later, when processing CPE compounds for electric wires and cables through compounding with inorganic additives and crosslinking agents, the surface is not smooth and rough, and the gloss is poor Bad appearance problems may appear.

In addition, the chlorinated polyethylene, the tensile strength (Tensile strength) measured by the method of ASTM D 412 is about 12 MPa or more, or about 12 MPa to about 30 MPa, or about 12.5 MPa or more, or about 12.3 MPa to about 20 MPa, or at least about 12.5 MPa or from about 12.5 MPa to about 15 MPa. The chlorinated polyethylene has a tensile elongation measured by the method of ASTM D 412 of about 500% or more, or about 500% to about 2000%, or about 700% or more, or about 700% to about 1500%, or about 900 % or more, or from about 900% to about 1200%.

Specifically, the pattern viscosity (MV, Mooney viscosity), tensile strength, and tensile elongation are from about 75 ^o C to about 85 ^o C in a slurry (water or HCl aqueous solution) state of about 500 kg to about 600 kg of polyethylene. ^o C to a final temperature of ^{about 140 o} C, after heating at a rate of ^{about 15 o} C/hr to about 18.5 ^{o C/hr, at a final temperature of about 120 o} C to about 140 ^o C for about 2 hours to about 5 hours It may be a value measured for chlorinated polyethylene obtained by performing a chlorination reaction with chlorine in gas phase. At this time, the chlorination reaction is performed by injecting gaseous chlorine while maintaining the pressure in the reactor at about 0.2 MPa to about 0.4 MPa at the same time as the temperature rises, and the total amount of chlorine input is about 650 kg to about 750 kg. have.

In addition, the chlorinated polyethylene has a hardness measured by the method of Shore A according to GB/T53 of about 50 or less, or about 40 or more to about 50 or less, or about 49 or less, or about 40 to about 49, or about 48 or less, or from about 40 to about 48, or from about 47 or less, or from about 41 to about 47, or from about 46 or less, or from about 42 to about 46, or from about 44 to about 46, or from about 44 to about 46. In particular, since the polyethylene of the present invention has a molecular structure in which a high crystal region is optimized, it is possible to improve processability by lowering the hardness of the chlorinated polyethylene.

Specifically, the hardness may be a value measured with chlorinated polyethylene obtained by performing the same chlorination reaction as when measuring Mooney viscosity (MV). For example, after processing chlorinated polyethylene at 135 ° C. for 5 minutes with a roll mill and manufacturing a sheet with a thickness of 6 mm at 140 ° C., it may be a value measured using this. .

In addition, the chlorinated polyethylene has a heat of fusion of 1.5 J/g or less, or about 0.1 J/g to about 1.5 J/g, or about 1.2 J/g or less, or about 0.2 J/g to about 1.2 J/g, or about 1.0 J/g or less, or about 0.3 J/g to about 1.0 J/g, or about 0.9 J/g or less, or about 0.4 J/g to about 0.9 J/g, or about 0.8 J/g or less or from about 0.4 J/g to about 0.8 J/g, or from about 0.7 J/g to about 0.8 J/g. In particular, the heat of fusion of the chlorinated polyethylene indicates the degree of residual crystals (DSC 1st heating, 30°C to 150°C peak), and the lower the residual crystals of the chlorinated polyethylene, the lower the hardness, and in the CPE compound Because of its excellent dispersibility, processability (comp'd MV) and size stability (plasticity) can be improved.

Specifically, the heat of fusion may be a value measured with chlorinated polyethylene obtained by performing the same chlorination reaction as when measuring Mooney viscosity (MV). In addition, the heat of fusion may be measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). As an example, heat flow change data generated while heating the DSC from -70 ℃ to 150 ℃ at a rate of 10 ℃ per minute is obtained. At this time, it is possible to obtain a heat of fusion value by integrating the peak appearing between 30 ℃ and 150 ℃ through the TA Universal Analysis program of TA instrument.

A method of measuring the MV, Mooney viscosity, hardness, heat of fusion, etc. of the chlorinated polyethylene is the same as described in Test Example 2, which will be described later, and a detailed measurement method is omitted.

The chlorinated polyethylene may have, for example, a chlorine content of about 20 wt% to about 50 wt%, about 31 wt% to about 45 wt%, or about 35 wt% to about 40 wt%. Here, the chlorine content of the chlorinated polyethylene may be measured using a combustion ion chromatography (Combustion IC, Ion Chromatography) analysis method. 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, the internal device temperature (Inlet temperature) 900 ^o C, the external Device temperature (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 o C.} In addition, the apparatus conditions and measurement conditions for measuring the chlorine content are the same as those described in Test Example 2 to be described later, and a detailed description thereof will be omitted.

Specifically, the chlorinated polyethylene according to the present invention has a Mooney viscosity (MV) of about 65 to about 80 as described above under the condition that the chlorine content is 35 wt% to 40 wt%, and has a tensile strength (Tensile strength) is about 12.5 MPa or more, or about 12.5 MPa to about 15 MPa, and the tensile elongation may be about 900% or more or about 900% to about 1200%.

The chlorinated polyethylene may be, for example, random chlorinated polyethylene.

The chlorinated polyethylene prepared according to the present invention is excellent in chemical resistance, weather resistance, flame retardancy, workability, etc., and thus is widely used for electric wires and cables.

On the other hand, according to another embodiment of the invention, there is provided a chlorinated polyethylene (CPE) compound comprising the chlorinated polyethylene as described above.

In particular, the chlorinated polyethylene (CPE) compound of the present invention optimizes both the polyethylene tangle molecular weight (Me) range and the melt flow index (MFRR _21.6/5 ) and realizes a high degree of crosslinking with a narrow molecular weight distribution, thereby reducing processability even during high-speed extrusion It has the characteristics of exhibiting very good mechanical properties while minimizing the

The chlorinated polyethylene (CPE) compound is mainly used for electric wires and cables, and has excellent processability, surface condition and gloss of molded products, and tensile strength of the cross-linked compound.

The chlorinated polyethylene (CPE) compound comprises about 1 wt% to about 80 wt%, about 10 wt% to about 70 wt%, about 20 wt% to about 60 wt% of the chlorinated polyethylene prepared by the method as described above can be done by

For example, the chlorinated polyethylene (CPE) compound is 100 parts by weight to 280 parts by weight of inorganic additives such as talc and carbon black, and 1 part by weight to 40 parts by weight of a crosslinking agent, based on 100 parts by weight of chlorinated polyethylene. may include.

As a specific example, the chlorinated polyethylene (CPE) compound includes 25% to 50% by weight of chlorinated polyethylene, 50% to 70% by weight of inorganic additives such as talc and carbon black, and 0.5% by weight of a crosslinking agent to 10% by weight.

The chlorinated polyethylene (CPE) compound is, for example, an inorganic additive (eg, Talc, Carbon black, etc.), a plasticizer, and a CPE compound with a crosslinking agent composition, crosslinked at 140 ^o C to 200 ^o C conditions, and then 100 ^o Mooney viscosity (MV) measured with a Mooney viscometer under C condition is from about 30 or more to about 48. Specifically, the imaginary chlorinated polyethylene (CPE) compound has a Mooney viscosity (MV) of at least about 32, or at least about 34, or at least about 33, or at least about 37, or at least about 37.5, or at least about 38; or about 38.5 or more, and about 45 or less, or about 46 or less, or about 45 or less, or about 43 or less, or about 41.5 or less, or about 40 or less, or about 39.5 or less, or about 39.2 or less. In addition, the chlorinated polyethylene (CPE) compound has a tensile strength measured by the method of ASTM D 412 of about 9.2 or more, or about 9.2 MPa to about 30 MPa, or about 9.4 MPa or more, or about 9.4 MPa to about 20 MPa, or at least about 9.5 MPa, or from about 9.5 MPa to about 15 MPa, or from about 9.5 MPa to about 12 MPa, or from about 9.5 MPa to about 10 MPa. The chlorinated polyethylene (CPE) compound has a tensile elongation measured by the method of ASTM D 412 of about 500% or more, or about 500% to about 1000%, or about 505% or more, or about 505% to about 800% , or about 510% or more, or about 510% to about 600%, or about 515% or more, or about 515% to about 550%, or about 520% or more, or about 520% to about 530%.

In addition, the chlorinated polyethylene (CPE) compound has a plasticity (Plasticity, %) of about 42% or more, or about 42% to about 65%, or about 43% or more, or about 43, measured by a method based on ASTM D 926 % to about 60%, or at least about 44%, or from about 44% to about 55%, or from about 44% to about 45.2%, or from about 44% to about 44.6%. The plasticity is a property that an object whose shape has been changed by an external force does not return to its original shape even when the external force is removed. The higher the plasticity, the better the workability and size stability. The chlorinated polyethylene (CPE) compound may have a plasticity of 42% or more in terms of realizing excellent extrusion size stability while ensuring excellent extrusion processing when processing for cable wires.

Specifically, the plasticity of the chlorinated polyethylene (CPE) compound ^{may be measured at 70 o} C and a load of 5 kg.

As an example, the plasticity of the chlorinated polyethylene (CPE) compound is measured using a CPE compound specimen having a height of 10 mm and a diameter of 16 mm (height h _{0 of the} specimen) 70 ^o C, 5 kg load condition, and _{, after measuring the height (h 1} ) of the deformed specimen by preheating at 70 ° C for 3 minutes and applying a load of 5 kg, the height of the specimen recovered after 3 minutes at room temperature after removing the load ( h ₂ ) is measured, and the degree of plasticity (Plasticity, %) of the CPE compound is calculated according to Equation 1 below.

[Formula 1]

P = (h ₀ -h ₂ ) / (h ₀ +h ₁ )

In the above formula 1,

P represents the plasticity (Plasticity, %) of the CPE compound,

h ₀ represents the height (mm) of the specimen before deformation when measuring the plasticity,

h ₁ is a value obtained by measuring the height (mm) of the deformed specimen by applying a load of 5 kg and preheating at 70 ° C for 3 minutes,

h ₂ represents the height (mm) of the specimen measured after 3 minutes at room temperature after the load was removed.

In addition, the method for manufacturing a molded article from chlorinated polyethylene according to the present invention can be applied to a conventional method in the art. For example, the chlorinated polyethylene may be roll-mill compounded and extruded to manufacture a molded article.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and thus the content of the present invention is not limited thereto.

<Example>

[Preparation of catalyst precursor]

Synthesis Example 1: Preparation of the first metallocene compound

_{Using 6-chlorohexanol, t-butyl-O-(CH 2} ) ₆ -Cl was prepared by the method described in the literature (Tetrahedron Lett. 2951 (1988)), and cyclopentadienyl sodium (NaCp) was added thereto. By reaction, t-butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80 ^o C/0.1 mmHg).

In addition, t-butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ ^{was dissolved in tetrahydrofuran (THF) at -78 o} C, n-butyllithium (n-BuLi) was slowly added thereto, and the temperature was raised to room temperature. Then, the reaction was carried out for 8 hours. The solution was again _{slowly added to a suspension solution of ZrCl 4} (THF) ₂ ^{(170 g, 4.50 mmol)/THF (30 mL) at -78 o} C, and the resulting lithium salt solution was further reacted at room temperature for 6 hours. made it All volatiles were removed by vacuum drying, and hexane was added to the obtained oily liquid material and filtered. After vacuum drying the filter solution, hexane was added to induce a precipitate at ^{low temperature (-20 o C).} The obtained precipitate was filtered at low temperature to obtain [t-butyl-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ ] in the form of a white solid (yield 92%).

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

¹³ C-NMR (CDCl ₃ ): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.31, 30.14, 29.18, 27.58, 26.00

Synthesis Example 2: Preparation of the second metallocene compound

2-1 Preparation of Ligand Compounds

8-methyl-5-(2-(trifluoromethyl)benzyl)-5,10-dihydroindeno[1,2-b]indole 2.9 g (7.4 mmol) was mixed with 100 mL of Hexane and 2 mL (16.8 mmol) of MTBE (methyl tertialry butyl ether), 3.2 mL (8.1 mmol) of a 2.5 M n-butyllithium (n-BuLi) hexane solution was added dropwise in a dryice/acetone bath, followed by stirring at room temperature overnight. In another 250 mL Schlenk flask, 2 g (7.4 mmol) of (6-tert-butoxyhexyl)dichloro(methyl)silane was dissolved in 50 mL of hexane, and then added dropwise in a dryice/acetone bath to 8-methyl-5- A lithiated slurry of (2-(trifluoromethyl)benzyl)-5,10-dihydroindeno[1,2-b]indole was added dropwise through a cannula. After the injection was completed, the mixture was slowly raised to room temperature and stirred at room temperature overnight. At the same time, 1.2 g (7.4 mmol) of fluorene was also dissolved in 100 mL of THF, and 3.2 mL (8.1 mmol) of a 2.5 M n-BuLi hexane solution was added dropwise in a dryice/acetone bath, followed by stirring at room temperature overnight.

Reaction solution of 8-methyl-5-(2-(trifluoromethyl)benzyl)-5,10-dihydroindeno[1,2-b]indole and (6-(tert-butoxy)hexyl)dichloro(methyl)silane (Si solution) was subjected to NMR sampling to confirm reaction completion.

¹ H NMR (500 MHz, CDCl ₃ ): 7.74-6.49 (11H, m), 5.87 (2H, s), 4.05 (1H, d), 3.32 (2H, m), 3.49 (3H, s), 1.50- 1.25 (8H, m), 1.15 (9H, s), 0.50 (2H, m), 0.17 (3H, d)

After confirming the synthesis, a lithiated solution of fluorene was slowly added dropwise to the Si solution in a dryice/acetone bath and stirred at room temperature overnight. After the reaction, extraction was performed with ether/water to _{remove residual moisture in the organic layer with MgSO 4 ,} and then the solvent was removed under vacuum and reduced pressure to obtain 5.5 g (7.4 mmol) of the ligand compound as an oil, which can be confirmed by ^{1 H-NMR.} could

¹ H NMR (500 MHz, CDCl ₃ ): 7.89-6.53 (19H, m), 5.82 (2H, s), 4.26 (1H, d), 4.14-4.10 (1H, m), 3.19 (3H, s), 2.40 (3H, m), 1.35-1.21 (6H, m), 1.14 (9H, s), 0.97-0.9 (4H, m), -0.34 (3H, t).

2-2 Preparation of metallocene compound

5.4 g (Mw 742.00 g/mol, 7.4 mmol) of the ligand compound synthesized in 2-1 above was dissolved in 80 mL of toluene and 3 mL (25.2 mmol) of MTBE, and 7.1 mL (17.8 mmol) of a 2.5 M n-BuLi hexane solution was dried on ice. It was added dropwise in /acetone bath and stirred at room temperature overnight. ZrCl ₄ (THF) ₂ 3.0 g (8.0 mmol) was added to 80 mL of toluene to prepare a slurry. ZrCl ₄ (THF) ₂ 80 mL of toluene slurry was transferred to a ligand-Li solution in a dry ice/acetone bath and stirred at room temperature overnight.

The reaction mixture was filtered to remove LiCl, and then toluene of the filtrate was removed by vacuum drying, and then 100 mL of hexane was added thereto, followed by sonication for 1 hour. This was filtered to obtain 3.5 g (yield 52 mol%) of a purple metallocene compound as a filtered solid.

¹ H NMR (500 MHz, CDCl ₃ ): 7.90-6.69 (9H, m), 5.67 (2H, s), 3.37 (2H, m), 2.56 (3H, s), 2.13-1.51 (11H, m), 1.17 (9H, s).

Synthesis Example 3: Preparation of the second metallocene compound

After transferring 50 g of Mg(s) to a 10 L reactor at room temperature, 300 mL of THF was added. After adding 0.5 g of I ₂ , the temperature of the reactor was maintained at ^{50 o 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. As 6-t-butoxyhexyl chloride was added, it was observed ^{that the reactor temperature increased from 4 o} C to 5 ^{o C.} Subsequently, 6-t-butoxyhexyl chloride was added and stirred for 12 hours to obtain a black reaction solution. After taking 2 mL of the resulting black solution, water was added to obtain an organic layer, and it ^{was confirmed that it was 6-t-butoxyhexane through 1} H-NMR, from which it was confirmed that the Grignard reaction proceeded well. From this, 6-t-butoxyhexyl magnesium chloride was synthesized.

After _{500 g of MeSiCl 3} and 1 L of THF were added to the reactor, the temperature of the reactor was cooled to ^{-20 o C.} 560 g of the previously synthesized 6-t-butoxyhexyl magnesium chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. After the Grignard reagent was fed, the reactor was stirred for 12 hours while slowly raising the temperature to room temperature, and it was confirmed that a _{white MgCl 2 salt was produced.} By adding 4 L of hexane, salt was removed through a labdori to obtain a filter dydddor. After adding the obtained filter solution to the reactor ^{, hexane was removed at 70 o} C to obtain a pale yellow liquid. It was confirmed that the obtained liquid was methyl (6-t-butoxyhexyl) dichlorosilane [methyl (6-t-butoxyhexyl) dichlorosilane] through ^{1 H-NMR.}

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

After adding 1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF to the reactor, the temperature of the reactor was cooled to ^{-20 o C.} 480 mL of n-BuLi was added to the reactor at a rate of 5 mL/min using a feeding pump. After adding n-BuLi, the reactor was stirred for 12 hours while slowly raising the temperature to room temperature. Then, an equivalent of methyl(6-t-butoxyhexyl)dichlorosilane (326 g, 350 mL) was quickly added to the reactor. After stirring for 12 hours while slowly raising the temperature of the reactor to room temperature, the temperature of the reactor ^{was cooled to 0 o} C again, and 2 equivalents of t-BuNH ₂ was added thereto. The reactor was stirred for 12 hours while slowly raising the temperature to room temperature. Then, THF was removed and 4 L of hexane was added to obtain a filter solution from which salt was removed through Labdory. After the filter solution was added to the reactor again, hexane ^{was removed at 70 o} C to obtain a yellow solution. It was confirmed that this was methyl(6-t-butoxyhexyl)(tetramethylCpH)t-butylaminosilane [methyl(6-t-butoxyhexyl)(tetramethylCpH)t-butylaminosilane] through ^{1 H-NMR.}

_{TiCl 3} (THF) ₃ 10 mmol in the dilithium salt of the ligand at ^{-78 o} C synthesized from n-BuLi and the ligand dimethyl(tetramethylCpH)t-butylaminosilane [dimethyl(tetramethylCpH)t-butylaminosilane] was added quickly. The reaction solution was stirred for 12 hours while ^{slowly raising the temperature from -78 o C to room temperature.} Then, at room temperature, an equivalent of PbCl ₂ (10 mmol) was added and stirred for 12 hours to obtain a dark blue solution with blue color. After removing THF from the resulting reaction solution, hexane was added to filter the product. After removing hexane from the obtained filter solution, it was confirmed by ¹ H-NMR that it was [tBu-O-(CH ₂ ) ₆ ](CH ₃ )Si(C ₅ (CH ₃ ) ₄ )(tBu-N)TiCl ₂ ]. .

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).

[Preparation of supported catalyst]

Preparation Example 1: Preparation of supported catalyst

5.0 kg of a toluene solution was put into a 20 L stainless steel (sus) high-pressure reactor, and the temperature of the reactor was maintained at ^{40 °C.} After ^{adding 1000 g of silica (SP948, manufactured by Grace Davison, SP948) dehydrated by applying vacuum at a temperature of 600 o} C for 12 hours to the reactor and sufficiently dispersing the silica, 84 g of the metallocene compound of Synthesis Example 1 was added to toluene. It was melted and ^{reacted by stirring at 40 o} C at 200 rpm for 2 hours. After that, stirring was stopped, settling for 30 minutes, and decantation of the reaction solution.

2.5 kg of toluene was added to the reactor, and 9.4 kg of a 10 wt% methylaluminoxane (MAO)/toluene solution was added, followed by ^{stirring at 40 o} C at 200 rpm for 12 hours. After the reaction, stirring was stopped, settling for 30 minutes, and the reaction solution was decanted. After adding 3.0 kg of toluene and stirring for 10 minutes, stirring was stopped and settling was performed for 30 minutes, and the toluene solution was decanted.

3.0 kg of toluene was put into the reactor, 116 g of the metallocene compound of Synthesis Example 2 was dissolved in 1 L of toluene solution, and put into the reactor, and ^{the reaction was stirred at 40 o} C at 200 rpm for 2 hours. At this time, the ratio of the metallocene compound of Synthesis Example 1 to the metallocene compound of Synthesis Example 2 was 42:58 by weight. After the reactor temperature was lowered to room temperature, stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decanted.

After adding 2.0 kg of toluene to the reactor and stirring for 10 minutes, the stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decanted.

3.0 kg of hexane was put into the reactor, the hexane slurry was transferred to a filter dry, and the hexane solution was filtered. It was dried under reduced pressure at ^{40 o} _{C for 4 hours to prepare 1 kg-SiO 2} hybrid supported catalyst.

Comparative Preparation Example 1: Preparation of Supported Catalyst

A hybrid supported catalyst was prepared in the same manner as in Preparation Example 1, except that the ratio of the metallocene compound of Synthesis Example 1 to the metallocene compound of Synthesis Example 2 was changed to 35:65 based on the weight.

Comparative Preparation Example 2: Preparation of Supported Catalyst

A hybrid supported catalyst was prepared in the same manner as in Preparation Example 1, except that the ratio of the metallocene compound of Synthesis Example 1 to the metallocene compound of Synthesis Example 2 was 60:40 based on the weight.

Comparative Preparation Example 3: Preparation of Supported Catalyst

A hybrid supported catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compound of Synthesis Example 3 was used instead of the metallocene compound of Synthesis Example 2.

[Production of polyethylene]

Example 1-1

High-density polyethylene was prepared by adding the supported catalyst prepared in Preparation Example 1 to a single slurry polymerization process.

First, 25 ton/hr of hexane, 10 ton/hr of ethylene, 120 ppm of hydrogen (relative to ethylene), and 10 kg/hr of triethylaluminum (TEAL) are injected into the reactor of ^{100 m 3 capacity, respectively, in Preparation Example 1} The hybrid supported metallocene catalyst according to the method was injected at 0.5 kg/hr. Accordingly, the ethylene was ^{continuously reacted in a hexane slurry state at a reactor temperature of 82 o} C and a pressure of 7.0 kg/cm ² to 7.5 kg/cm ² , and then subjected to a solvent removal and drying process to prepare high-density polyethylene in powder form.

Example 1-2

It was prepared in the same manner as in Example 1-1, except that the amount of hydrogen was changed to 125 ppm to prepare high-density polyethylene in powder form.

Examples 1-3

It was prepared in the same manner as in Example 1-1, except that the amount of hydrogen was changed to 130 ppm to prepare high-density polyethylene in powder form.

Comparative Example 1-1

Commercially available high-density polyethylene (HDPE) products (Z/N-1, CE2030K, LG Chem) prepared using a Ziegler-Natta catalyst and having a MI ₅ ( ^{melt index measured at 190 o C, a load of 5 kg) of 1.7 g/10 min.} ) was prepared in Comparative Example 1-1.

Comparative Example 1-2

Commercially available high-density polyethylene (HDPE) products (Z/N-2, CE2080, LG Chem) prepared using a Ziegler-Natta catalyst and having an MI ₅ ( ^{melt index measured at 190 o C, 5 kg load) of 1.2 g/10 min.} ) was prepared in Comparative Example 1-2.

Comparative Example 1-3

A high-density polyethylene (HDPE) pilot product (Z/N-3, LG Chem) prepared using a Ziegler-Natta catalyst and having an MI ₅ ( ^{melt index measured at 190 o C, 5 kg load) of 1.5 g/10 min was obtained.} It was prepared in Comparative Example 1-3.

Comparative Example 1-4

Prepared in the same manner as in Example 1-2, but using the supported catalyst prepared in Comparative Preparation Example 1 instead of the supported catalyst prepared in Preparation Example 1, the high-density polyethylene of Comparative Example 1-4 was prepared in powder form .

Comparative Example 1-5

Prepared in the same manner as in Example 1-2, but using the supported catalyst prepared in Comparative Preparation Example 2 instead of the supported catalyst prepared in Preparation Example 1, the high-density polyethylene of Comparative Example 1-5 was prepared in powder form .

Comparative Example 1-6

Prepared in the same manner as in Example 1-1, but using the supported catalyst prepared in Comparative Preparation Example 3 instead of the supported catalyst prepared in Preparation Example 1, the high-density polyethylene of Comparative Example 1-6 was prepared in powder form .

Test Example 1

For the polyethylene prepared in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-6, physical properties were measured in the following manner, and the results are shown in Table 1 below.

1) Melt index (MI, g/10 min):

_{The melt index (MI 5} , MI _21.6 ) was measured under the conditions of loads of 2.16 kg, 5 kg, and 21.6 kg at a ^{temperature of 190 o} C, respectively, by the method of ASTM D 1238, and the weight of the polymer melted for 10 minutes (g) indicated as

2) melt flow index (MFRR, MI) _21.6/5 ):

By the method of ASTM D 1238 to the melt index measured at 190 ^o C, 21.6 kg load was sancheuk to 190 ^o C, the melt flow divided by the melt index measured at 5 kg load index (MFRR, MI _{21.6 / 5)} .

3) Density:

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

4) Proportion of highly crystalline region (%):

After measuring for polyethylene to obtain a temperature rise elution fractionation (TREF) graph, on the TREF graph, using the elution temperature of 105 ^o C as the ordinate of the high-crystal region as a reference, high crystals corresponding to ^{the elution temperature of 105 o C or higher} The graph area of the region was measured, and a percentage value obtained by dividing it by the total graph area was expressed as a high crystal region ratio (%). Here, the temperature rise elution fractionation (TREF) graph of polyethylene was obtained through an Agilent Technologies 7890 A instrument from PolymerChar. More specifically, after dissolving a polyethylene sample at a concentration of 1.5 mg/mL in 20 mL of 1,2,4-trichlorobenzene, it was dissolved while raising the temperature from ^{30 o} C to 150 ^o C at ^{a rate of 40 o C/min.} Then, the graph was obtained through recrystallization while lowering the temperature to ^{35 o} C at ^{a rate of 0.5 o} C/min, and eluting while raising the temperature at a rate of 1 ^{o C/min to 140 o C again.}

5) molecular weight distribution (MWD, polydispersity index):

The weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene are measured using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water), and the molecular weight distribution (MWD) by dividing the weight average molecular weight by the number average molecular weight ) was calculated.

Specifically, as a gel permeation chromatography (GPC) apparatus, a Waters PL-GPC220 instrument was used, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. At this time, the measurement temperature was 160 ^o C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) was used as a solvent, and the flow rate was 1 mL/min. Polyethylene samples according to Examples and Comparative Examples were pretreated by dissolving each of them in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160 ^{o C for 10 hours using a GPC analysis device (PL-GP220).} , was prepared at a concentration of 10 mg/10 mL, 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 the polystyrene standard specimen is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 400000 g/mol, 1000000 g Nine species of /mol were used.

Example comparative example 1-1 1-2 1-3 1-1 1-2 1-3 1-4 1-5 1-6 catalyst production example
One production example
One production example
One Z/N-1 Z/N-2 Z/N-3 compare
production example
One compare
production example
2 compare
production example
3 _{H 2} input amount during polymerization (ppm) 120 125 130 - - - 230 80 120 MI _2.16 (2.16 kg, 190 ^o C, g/10 min) 0.30 0.31 0.32 0.41 0.32 0.30 0.34 0.15 0.85 MI ₅ (5 kg, 190 ^o C, g/10 min) 1.1 1.3 1.4 1.7 1.2 1.5 1.5 0.6 3.0 MFRR (21.6/5) 19 19.5 20 17.5 15.6 17.2 22 16 10.5 Density (g/cm ³ ) 0.957 0.958 0.959 0.958 0.958 0.957 0.959 0.955 0.955 High Crystalline Area Ratio
(wt%, TREF, over 105℃) 7.6 7.7 7.8 18 11.2 7.9 8.2 7.5 5.3 Mw (×10 ³ g/mol) 153 150 147 175 180 177 146 179 93 Molecular weight distribution (Mw/Mn) 7.2 7.4 7.6 15.5 9.1 15.2 8.6 6.4 3.9

First, in Table 1, H ₂ input amount (ppm) during polymerization represents the hydrogen gas content based on the ethylene input amount.

As shown in Table 1, in comparison with Comparative Examples, the CPE MVs of the Examples are all optimized to 50 to 60 by MI, MFRR and molecular structure, and excellent extrusion even in high-speed extrusion processes when applied to wires and cables. It can be seen that mechanical properties such as tensile strength can be excellent along with processability and size stability.

Test Example 2

Chlorinated polyethylene was prepared using the polyethylene prepared in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-6.

[Production of chlorinated polyethylene]

5000 L of water and 550 kg of the high-density polyethylene prepared in Example 1-1 were put into the reactor, sodium polymethacrylate as a dispersant, oxypropylene and oxyethylene copolyether as an emulsifier, and benzoyl peroxide as a catalyst, After raising the temperature from 80 ^o C to 132 ^o C at a ^{rate of 17.3 o} C/hr, it was chlorinated with gaseous chlorine at a ^{final temperature of 132 o C for 3 hours.} At this time, gaseous chlorine was injected while maintaining the pressure in the reactor at 0.3 MPa at the same time as the temperature was raised, and the total amount of chlorine input was 610 kg. The chlorinated reactant was added to NaOH to neutralize 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, for the polyethylenes prepared in Examples 1-2 to 1-3 and Comparative Examples 1-1 to 1-6, chlorinated polyethylene in powder form was prepared in the same manner as above.

As described above, using the polyethylene prepared in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-6, Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2 The physical properties of -6 chlorinated polyethylene were measured in the following manner, and the results are shown in Table 2 below.

1) MV (Mooney viscosity) of CPE:

Wrap the rotor in the Mooney viscometer with the CPE sample and close the die. After preheating to 121 ^o C for 1 min, the rotor was rotated for 4 min ^{to measure MV (Mooney viscosity, 121 o} C, ML1+4).

2) Hardness of CPE:

The hardness of CPE was measured by the method of Shore A according to GB/T53. Specifically, after processing a chlorinated polyethylene (CPE) powder product at 135 ° C. for 5 minutes with a roll mill, and after producing a sheet of 6 mm thickness at 140 ° C. Therefore, hardness was measured by the method of Shore A according to GB/T53.

3) CPE heat of fusion (J/g):

The heat of fusion of CPE was measured using a differential scanning calorimeter (Differential Scanning Calorimeter, DSC, device name: DSC 2920, manufacturer: TA instrument).

Specifically, the heat of fusion (J/g) indicates the degree of residual crystal (DSC 1st heating, 30 ℃ ~ 150 ℃ peak), and the temperature of the DSC is increased from -70 ℃ to 150 ℃ at a rate of 10 ℃ per minute Get the heat flow change data generated while doing it. At this time, the heat of fusion value was obtained by integrating the peak appearing between 30°C and 150°C through the TA Universal Analysis program of TA instrument. At this time, the rate of temperature rise and fall was 10 ^o C/min, and the heat of fusion was measured in the section where the first temperature rose.

Example comparative example 2-1 2-2 2-3 2-1 2-2 2-3 2-4 2-5 2-6 MV of CPE (121 ^o C, ML1+4) 54 53 52 57 72 53 45 65 53 Hardness of CPE (Shore A) 46 45 44 49 48 50 45 46 52 CPE heat of fusion (J/g) 0.8 0.7 0.8 14.4 4.9 2.2 One 0.8 20.5

As shown in Table 2, as compared to Comparative Examples, the Examples have a Mooney viscosity (MV) of 52 to 54 of CPE, and a heat of fusion of 0.7 J/g to 0.8 J/g, resulting in residual crystals (DSC). 1st heating, 30 ℃ ~ 150 ℃ peak) is small), the chlorine distribution is uniform, and accordingly, it can be seen that the hardness is low as 44 to 46. In particular, in comparison with Comparative Example 2-3, which has an MV equivalent to that of Examples, the heat of fusion of CPE is lower than about 63% in Examples 2-1 and 2-3, and Example 2-2 is about It is lower than 68% and excellent processability can be realized. In addition, in Comparative Examples 2-6, the hardness or heat of fusion should be lowered due to the small proportion of high crystalline region, but the molecular weight of polyethylene is too low, so the hardness and heat of fusion significantly increase, and the chlorination productivity is greatly reduced so that the chlorination reaction is properly performed It was confirmed that it was not supported.

Test Example 3

25 to 50 wt% of chlorinated polyethylene prepared by using the polyethylene prepared in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-5, and talc, carbon black, etc. 50 to 70% by weight of the inorganic additive and 0.5 to 10% by weight of the crosslinking agent were mixed and then processed to prepare CPE compound specimens of Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-5.

As described above, Examples 3-1 to 3-3 and Comparative Example 3, including the chlorinated polyethylene prepared from the polyethylene prepared in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-5 The physical properties of the CPE compounds of -1 to 3-5 were measured in the following manner, and the results are shown in Table 3 below.

1) MV (Mooney viscosity) of CPE compound:

Wrap the rotor in the MV device with the CPE compound sample and close the die. After preheating to 100 ^o C for 1 min, the rotor was rotated for 4 min ^{to measure MV (Mooney viscosity, 100 o} C, ML1+4).

2) Tensile strength (MPa) and tensile elongation (%) of CPE compound:

The tensile strength (Tensile strength, MPa) and tensile elongation (%) of the CPE compound under 500 mm/min conditions were measured by a method according to ASTM D 412.

3) Plasticity (%) of CPE compound:

According to ASTM D 926, the plasticity (Plasticity, %) of the CPE compound was measured at ^{70 o C and 5 kg load condition.}

Specifically, using a CPE compound specimen having a height of 10 mm and a diameter of 16 mm (height h0 of the specimen) ^{was measured at 70 o} C and 5 kg load, 70 ° C preheating for 3 minutes and loading _{(Load) After measuring the height (h 1} ) of the deformed specimen by applying a load of 5 kg, removing the load and measuring the height (h ₂ ) of the recovered specimen after 3 minutes at room temperature, CPE according to the following formula 1 The plasticity (Plasticity, %) of the compound was calculated.

[Formula 1]

P = (h ₀ -h ₂ ) / (h ₀ +h ₁ )

In the above formula 1,

P represents the plasticity (Plasticity, %) of the CPE compound,

h ₀ represents the height (mm) of the specimen before deformation when measuring the plasticity,

h ₁ is a value obtained by measuring the height (mm) of the deformed specimen by applying a load of 5 kg and preheating at 70 ° C for 3 minutes,

h ₂ represents the height (mm) of the specimen measured after 3 minutes at room temperature after the load was removed.

Example comparative example 3-1 3-2 3-3 3-1 3-2 3-3 3-4 3-5 MV of CPE compound (100 ^o C, ML1+4) 39.2 38.9 38.5 40.7 55.8 41.6 34.6 50 Tensile strength of CPE compound (MPa) 10 10 9.5 9 12 9 9 10 Tensile Elongation of CPE Compound (%) 520 520 530 490 480 490 530 520 Plasticity of CPE compound (%) 44.3 44.6 44.1 36.7 38.5 40.3 41.9 45.8

As shown in Table 3, in comparison with Comparative Examples, the MV (Mooney viscosity) of the CPE compound was 38.5 to 39.2, and the tensile strength and elongation were also very excellent at 9.5 MPa to 10 MPa and 520% to 530%. , It can be seen that the plasticity is very excellent in 44.1% to 44.6%. Accordingly, it can be seen that the embodiments according to the present invention have product specifications in which chloride productivity, MV, processability, tensile strength, and plasticity are all balanced.

On the other hand, the CPE compounds of Comparative Examples 3-1, 3-3, and 3-4 may have poor tensile strength and poor mechanical properties when processed for use in wires and cables. In particular, the CPE compound of Comparative Examples 3-4 has a low CPE MV, resulting in lower tensile strength, and the CPE compounds of Comparative Examples 3-2 and 3-5 have a high CPE MV. Extrusion processability may be poor.

Claims (15)

MI ₅ ( ^{melt index measured at 190 o} C, 5 kg load) is 0.8 g/10 min to 1.4 g/10 min,
The melt flow index (MFRR _21.6/5 , the melt index measured at ^{190 o} C, 21.6 kg load by the method of ASTM D 1238 ^{divided by the melt index measured at 190 o} C, 5 kg load) is 18 to 22,
On the temperature rise elution fractionation (TREF) graph, the ratio of the high crystalline region representing the percentage value obtained by dividing the graph area of the high crystalline region corresponding to the ^{elution temperature of 105 o C or higher by the total graph area is 10% or less,}
polyethylene.
According to claim 1,
The polyethylene is an ethylene homopolymer,
polyethylene.
According to claim 1,
The polyethylene has a MI of _2.16 ( ^{melt index measured at 190 o} C, 2.16 kg load) of 0.01 g/10 min to 0.45 g/10 min,
polyethylene.
According to claim 1,
The polyethylene, the proportion of the high crystalline region is 3% to 10%,
polyethylene.
According to claim 1,
The polyethylene has a density of 0.955 g/cm ³ to 0.960 g/cm ³ ,
polyethylene.
According to claim 1,
The polyethylene has a molecular weight distribution (Mw / Mn) of 5 to 10,
polyethylene.
According to claim 1,
The polyethylene has a weight average molecular weight of 110000 g / mol to 250000 g / mol,
polyethylene.
at least one first metallocene compound represented by the following formula (1); and polymerizing ethylene in the presence of at least one second metallocene compound selected from compounds represented by the following Chemical Formula 2,
The method for producing polyethylene according to any one of claims 1 to 7, wherein the weight ratio of the first metallocene compound and the second metallocene compound is 40:60 to 45:55:
[Formula 1]

In Formula 1,
Any one or more of R ₁ to R _{8 is -(CH 2} ) _n -OR, wherein R is C _1-6 straight or branched chain alkyl, n is an integer from 2 to 6,
The _{rest of R 1} to R ₈ are the same as or different from each other and are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-40 alkylaryl, C _{7- 40 It} is a functional group selected from the group consisting of arylalkyl, or two or more adjacent to each other are connected to each other to form a C _6-20 aliphatic or aromatic ring _{unsubstituted or substituted with a C 1-10 hydrocarbyl group,} ,
Q ₁ and Q ₂ are the same as or different from each other, and each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkoxyalkyl, C _6-20 aryl, C _7-40 alkyl aryl, C _7-40 arylalkyl;
A ₁ is carbon (C), silicon (Si), or germanium (Ge);
M ₁ is a Group 4 transition metal;
X ₁ and X ₂ are the same as or different from each other, and each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, nitro group, amido group, C _1-20 alkylsilyl, C _1-20 alkoxy, or C _1-20 sulfonate group;
m is an integer of 0 or 1,
[Formula 2]

In Formula 2,
Q ₃ and Q ₄ are the same as or different from each other, and each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkoxyalkyl, C _6-20 aryl, C _7-40 alkyl aryl, C _7-40 arylalkyl;
A ₂ is carbon (C), silicon (Si), or germanium (Ge);
M ₂ is a Group 4 transition metal;
X ₃ and X ₄ are the same as or different from each other, and each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, nitro group, amido group, C _1-20 alkylsilyl, C _1-20 alkoxy, or C _1-20 sulfonate group;
C ₁ and C ₂ is one of which is represented by Formula 3a or Formula 3b, C ₁ and The _{other one of C 2} is represented by Formula 3c, Formula 3d, or Formula 3e;
[Formula 3a]

[Formula 3b]

[Formula 3c]

[Formula 3d]

[Formula 3e]

In Formulas 3a, 3b, 3c, 3d and 3e, R ₉ to R ₂₁ and R _17' to R _21' are the same as or different from each other, and each independently hydrogen, halogen, C _1-20 alkyl, C _1-20 Haloalkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 arylalkyl, provided that at least one of _{R 17} to R ₂₁ and R _17′ to R _{21′ is C 1-20} haloalkyl;
R ₂₂ to R ₃₉ are the same as or different from each other, and each independently hydrogen, halogen, C _1-20 alkyl, C _1-20 haloalkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 arylalkyl, or two adjacent _{R 22} to R ₃₉ or more may be connected to each other to form a C _6-20 aliphatic or aromatic ring _{substituted or unsubstituted with a C 1-10 hydrocarbyl group;}
* indicates a site binding to _{A 2} and M _{2 .}
9. The method of claim 8,
The first metallocene compound is represented by any one of the following formulas 1-1 to 1-4,
Process for making polyethylene:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
Q ₁ , Q ₂ , A ₁ , M ₁ , X ₁ , X ₂ , and R ₁ to R ₈ are as defined in claim 8,
R' and R'' are the same as or different from each other and each independently represent a C _1-10 hydrocarbyl group.
9. The method of claim 8,
R ₃ and R ₆ are each C _1-6 alkyl, or _{C 2-6} alkyl substituted with C _{1-6 alkoxy;}
Method for producing polyethylene.
9. The method of claim 8,
The second metallocene compound is represented by the following formula 2-1,
Process for making polyethylene:
[Formula 2-1]

In Formula 2-1,
Q ₃ , Q ₄ , A ₂ , M ₂ , X ₃ , X ₂₄ , R ₁₁ , and R ₁₇ to R ₂₉ are as defined in claim 8 .
9. The method of claim 8,
R ₁₇ to R ₂₁ and R _17′ to R _21′ are each hydrogen or C _1-6 haloalkyl, provided that at least one of _{R 17} to R ₂₁ and R _17′ to R _{21′ is C 1-6} halo alkyl,
sign,
Method for producing polyethylene.
9. The method of claim 8,
The polymerization step consists of introducing 100 ppm to 150 ppm of hydrogen gas based on the ethylene content,
Method for producing polyethylene.
A chlorinated polyethylene prepared by reacting the polyethylene of any one of claims 1 to 7 with chlorine.
15. The method of claim 14,
The chlorinated polyethylene has a pattern viscosity (MV, Mooney viscosity) of 50 to 60 measured under ^{121 o C condition,}
Hardness measured by Shore A method according to GB/T53 is 50 or less,
The heat of fusion according to the residual crystal (DSC 1st heating, 30 ℃ to 150 ℃ peak) is 1.5 J / g or less,
Chlorinated polyethylene.

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