KR102578777B1 - Polyethylene and its chlorinated polyethylene - Google Patents

Abstract

Polyethylene according to the present invention realizes a high middle molecular region in the molecular structure, facilitates deoxidation, dehydration, and drying processes during chlorination processing, and increases chlorination productivity by enabling an increase in chlorination temperature, which reacts with chlorine. By doing this, chlorinated polyethylene with excellent chlorination productivity and thermal stability can be produced.

Description

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

The present invention relates to polyethylene and its chlorinated polyethylene, which can increase chlorination productivity by implementing a high middle molecular region in the molecular structure, facilitating deoxidation, dehydration, and drying processes during chlorination processing, and enabling an increase in chlorination temperature.

Chlorinated polyethylene (CPE, Chlorinated Polyethylene), manufactured by reacting polyethylene and chlorine, is known to have improved physical and mechanical properties compared to polyethylene, and can withstand particularly harsh external environments, making it suitable for use in various containers, fibers, pipes, etc. It is used as a packing material and electric heating material.

Chlorinated polyethylene is generally manufactured by putting polyethylene in a suspension and reacting it with chlorine, or by placing polyethylene in an aqueous HCl solution and reacting it with chlorine to replace the hydrogen in polyethylene with chlorine. Through this process of chlorination of polyethylene, CPE acquires rubber-like properties.

In order to fully express the properties of chlorinated polyethylene, chlorine must be uniformly substituted in polyethylene, which is affected by the properties of polyethylene that reacts with chlorine. In particular, chlorinated polyethylene such as CPE (Chlorinated Polyethylene) is widely used for wires and cables through compounding with inorganic additives and crosslinking agents, and the strength of the compound varies depending on the physical properties of chlorinated polyethylene.

Additionally, chlorinated polyethylene can generally be manufactured by reacting polyethylene with chlorine in a suspension state, or by reacting polyethylene with chlorine in an aqueous HCl solution. Specifically, when producing CPE, it goes through the processes of chlorination, deoxidation, dehydration, and drying. If the crystal structure of polyethylene is not maintained stably, the crystal structure collapses through a high-temperature chlorination reaction and the pores of the polyethylene particles form. It can get clogged. In the process after deoxidation, washing with water is required to remove residual HCl in the polyethylene particles, but if the pores are clogged, the overall production time is delayed due to the delay in deoxidation time, which reduces chlorination productivity. In particular, as the melting of the polyethylene chain becomes more severe as the temperature rises within the chlorination process, blocking occurs where the particles melt together and form a lump, and as swelling occurs, water is trapped inside, which increases the drying time after chlorination. This will take a long time. Due to this phenomenon, it is known that the productivity of a CPE company's CPE is superior as the washing and drying time and efficiency in the chlorination stage are improved.

Accordingly, it is necessary to secure optimized physical properties of chlorinated polyethylene in order to improve its excellent strength when compounding for wires and cables and to improve processability when extruding. In addition, to improve productivity in the chlorination process, it is necessary to develop a molecular structure with many middle molecular regions. There is a continued need for the development of technology to produce polyethylene.

The present invention seeks to provide polyethylene and a method for producing the same, which can produce chlorinated polyethylene with excellent strength and improved processability during extrusion by realizing a high middle molecular region in the molecular structure.

In addition, the present invention seeks to provide chlorinated polyethylene prepared by reacting the polyethylene with chlorine and a PVC composition containing the same.

According to one embodiment of the invention, the melt index MI ₅ (measured at 190 ^o C, at a load of 5 kg) is less than or equal to 0.55 g/10 min, and the melt index MI _21.6 (measured at 190 ^o C, at a load of 21.6 kg) is less than or equal to 6 g/10 min. It is 10min or less, and the complex viscosity (η*(ω0.05), complex viscosity) measured at a frequency (ω) of 0.05 rad/s is more than 68000 Pa·s, and at a frequency (ω) of 500 rad/s. Polyethylene having a measured complex viscosity (η*(ω500), complex viscosity) of 900 Pa·s to 1600 Pa·s is provided.

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

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

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

The polyethylene according to the present invention has a high middle molecular region in the molecular structure, and can be reacted with chlorine to produce chlorinated polyethylene with excellent chlorination productivity and thermal stability.

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

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

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

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

According to one embodiment of the invention, polyethylene is provided that can produce chlorinated polyethylene with excellent strength and improved processability during extrusion by implementing a molecular structure with a high middle molecular region.

The polyethylene has a melt index MI ₅ (measured at 190 ^o C, 5 kg load) of 0.55 g/10 min or less, and a melt index MI _21.6 (measured at 190 ^o C, 21.6 kg load) of 6 g/10 min or less, Complex viscosity (η*(ω0.05), complex viscosity) measured at frequency (ω) 0.05 rad/s is more than 68000 Pa·s, and complex viscosity measured at frequency (ω) 500 rad/s (η*(ω500), complex viscosity) is characterized in that it is 900 Pa·s to 1600 Pa·s.

In general, chlorinated polyethylene is manufactured by reacting polyethylene with chlorine, meaning that some of the hydrogen in polyethylene is replaced with chlorine. When hydrogen in polyethylene is replaced with chlorine, the properties of polyethylene change because the atomic volumes of hydrogen and chlorine are different. For example, chlorination productivity and thermal stability increase. In particular, the smaller and more uniform the overall size of the chlorinated polyethylene particles are, the easier it is for chlorine to penetrate into the center of the polyethylene particles, so the degree of chlorine substitution within the particles is uniform and can exhibit excellent physical properties. To this end, the polyethylene according to the present invention has a high and medium concentration in the molecular structure. It is possible to provide chlorinated polyethylene with excellent strength and improved processability during extrusion due to its high molecular area.

The polyethylene of the present invention has a high middle molecular region in the molecular structure, optimizing the melt index MI ₅ (measured at 190 ^o C, 5 kg load) and MI _21.6 (measured at 190 ^o C, 21.6 kg load), and at the same time, low frequency It is characterized by maximizing the complex viscosity in this region and maintaining the optimal range of complex viscosity in the high frequency region. As a result, the heavy molecular content of polyethylene increases, and chlorinated polyethylene with excellent chlorination productivity, thermal stability, and mechanical properties can be manufactured.

The polyethylene according to the present invention may be high-density polyethylene (HDPE), for example, an ethylene homopolymer.

As described above, the polyethylene has a melt index MI ₅ of about 0.55 g/10min or less, or about 0.1 g/10min to about 0.55 g/10min, as measured by the method of ASTM D 1238 under the conditions of a temperature of 190 ^o C and a load of 5 kg. It may be about 0.4 g/10min or less, or about 0.1 g/10min to about 0.4 g/10min, or about 0.35 g/10min or less, or about 0.21 g/10min to about 0.35 g/10min. In addition, the high load melt index MI _21.6 measured under the condition of 21.6 kg, together with the melt index MI ₅ measured under the condition of 5 kg, is about 6 g/10min or less or about 2.2 g/10min to about 6 g/10min. It may be about 5.8 g/10min or less, or about 2.5 g/10min to about 5.8 g/10min, or about 5.5 g/10min or less, or about 2.8 g/10min to about 5.5 g/10min. If either of these melt indices MI ₅ and MI _21.6 is too high, the content of low molecules increases and the shape of the particles increases, such as low molecules melting at high temperatures and forming lumps during the chlorination process, resulting in poor thermal stability. Accordingly, the melt indices MI ₅ and MI _21.6 should be about 0.55 g/10min or less and about 6 g/10min or less, respectively, in terms of realizing excellent thermal stability. However, the lower the melt index MI ₅ and MI _21.6 , the higher the viscosity, so that when manufacturing chlorinated polyethylene, physical properties such as pattern viscosity fall outside the optimal range, and in this case, problems with poor dispersion of inorganic substances may occur. Accordingly, the melt indices MI ₅ and MI _21.6 can be about 0.1 g/10min or more and about 2.2 g/10min or more, respectively, in terms of reducing the extrusion processing load during product processing and securing excellent external physical properties.

In addition, the polyethylene of the present invention optimizes the melt index MI ₅ and MI _21.6 as described above, and at the same time has a melt flow rate (MFRR _21.6/5 , measured at 190 ^o C and 21.6 kg load by the method of ASTM D 1238). It is desirable to optimize the melt index (melt index divided by the melt index measured at 190 ^o C and 5 kg load). At this time, the melt flow index of the polyethylene (MFRR _21.6/5 , the melt index measured at 190 ^o C and 21.6 kg load by the method of ASTM D 1238 divided by the melt index measured at 190 ^o C and 5 kg load) may be from about 10 to about 18. Specifically, the melt flow index may be from about 10 to about 16, or from about 12 to about 15.5, or from about 13.1 to about 15.2. The melt flow index may be about 10 or more in terms of processability during extrusion, and may be about 18 or less in terms of securing excellent mechanical properties by increasing the Mooney viscosity (MV) of CPE.

In particular, the polyethylene is manufactured by optimizing hydrogen input conditions using a specific metallocene catalyst and process conditions, as will be described later, and optimizing the complex viscosity according to a specific frequency along with the melt index described above. By increasing the molecular area, deoxidation, dehydration, and drying processes can be facilitated during chlorination processing, and chlorination productivity can be increased by enabling an increase in chlorination temperature, thereby improving the strength of the final product, CPE compound.

The polyethylene has a complex viscosity (η*(ω0.05), complex viscosity) measured at a frequency (ω) of 0.05 rad/s of about 68,000 Pa·s or more or about 68,000 Pa·s to about 180,000 Pa·s. appears high. Specifically, the complex viscosity (η*(ω0.05), complex viscosity) measured at the frequency (ω) 0.05 rad/s is about 70000 Pa·s or more or about 70000 Pa·s to about 160000 Pa·s. , or about 75,000 Pa·s or more, or about 75,000 Pa·s to about 150,000 Pa·s, or about 79,000 Pa·s or more, or about 79,000 Pa·s to about 115,000 Pa·s. In addition, the complex viscosity (η*(ω500), complex viscosity) measured at a frequency (ω) of 500 rad/s shows an optimal range of about 900 Pa·s to about 1600 Pa·s. Specifically, the complex viscosity (η*(ω500), complex viscosity) measured at a frequency (ω) of 500 rad/s is about 580 Pa·s to about 1000 Pa·s to about 1500 Pa·s, or about 1050 Pa·s. It may be Pa·s to about 1480 Pa·s. Here, the complex viscosity (η*(ω0.05), complex viscosity) measured at the frequency (ω) of 0.05 rad/s should be about 68000 Pa·s or more in terms of improving the chlorination productivity of polyethylene. In addition, the complex viscosity (η*(ω500), complex viscosity) measured at the frequency (ω) of 500 rad/s is in terms of ensuring that the processing load is appropriately maintained when polyethylene is extruded for processing compound products after the chlorination process. The range as described above must be maintained.

Specifically, the complex viscosity can be measured using a rotational rheometer, for example, TA instruments' rotational rheometer ARES (Advanced Rheometric Expansion System, ARES G2). Polyethylene samples were placed at 190 ^o C using parallel plates with a diameter of 25.0 mm so that the gap was 2.0 mm. The measurement is in dynamic strain frequency sweep mode, and a total of 41 points can be measured, with a strain of 5% and a frequency of 0.05 rad/s to 500 rad/s, 10 points for each decade.

In general, completely elastic materials deform in proportion to elastic shear stress, which is called Hooke's law. Additionally, in the case of a pure viscous liquid, deformation occurs in proportion to the viscous shear stress, which is called Newton's law. In a completely elastic material, the deformation can be recovered when elastic energy is accumulated and the elastic shear stress is removed, but in a completely viscous material, the deformation is not recovered even if the viscous shear stress is removed because all the energy is dissipated through deformation. Additionally, the viscosity of the material itself does not change.

However, polymers have properties intermediate between fully elastic substances and viscous liquids in the molten state, which is called viscoelasticity. In other words, when a polymer undergoes shear stress in a molten state, its deformation is not proportional to the shear stress, and it also has the characteristic of changing viscosity depending on the shear stress, which is also called a non-Newtonian fluid. These characteristics are due to the complexity of deformation due to shear stress due to the polymer's large molecular size and complex intermolecular structure.

In particular, when manufacturing molded products using polymers, shear thinning is an important consideration among the characteristics of non-Newtonian fluids. The shear fluidization phenomenon refers to a phenomenon in which the viscosity of a polymer decreases as the shear rate increases. The molding method of the polymer is determined according to these shear fluidization characteristics. In particular, when manufacturing large molded products such as large-diameter pipes or composite pipes or molded products that require high-speed polymer extrusion, as in the present invention, significant pressure must be applied to the molten polymer, so it is difficult to manufacture such molded products if they do not exhibit shear fluidization characteristics. Fluidization characteristics are important considerations.

Accordingly, in the present invention, shear fluidization characteristics are measured through complex viscosity (η*[Pa.s]) according to frequency (ω[rad/s]). In particular, by optimizing the complex viscosity at frequencies (ω) of 0.05 rad/s and 500 rad/s, excellent chlorination productivity and excellent physical properties of the compound can be realized. In addition, the range of physical properties such as pattern viscosity (MV) of chlorinated polyethylene can be predicted through complex viscosity at a frequency (ω) of 500 rad/s.

In particular, polyethylene, which is made with a molecular structure optimized by complex viscosity according to a specific frequency along with melt index according to the present invention, can minimize particle changes due to high temperature during chlorination processing at high temperature, improving thermal stability. This prevents clumping and clumping, and as particle changes are minimized, chlorine is distributed evenly, thereby improving the tensile strength of the compound.

Meanwhile, the polyethylene may have a density of about 0.947 g/cm ³ or more. Specifically, the density of the polyethylene is about 0.947 g/cm ³ or more, or about 0.947 g/cm ³ to about 0.954 g/cm ³ , or about 0.948 g/cm ³ or more, or about 0.948 g/cm ³ to about 0.953 g/ cm ³ , or about 0.950 g/cm ³ or more, or about 0.950 g/cm ³ to about 0.951 g/cm ³ . This means that the content of the crystalline part in the polymer structure of polyethylene is high and dense, which makes it difficult for changes in the crystal structure to occur during the chlorination process. In particular, when the density of the polyethylene is less than about 0.947 g/cm ³ , the crystallinity of the particles decreases, which reduces thermal stability, and the shape of the particles increases during the chlorination process, resulting in the formation of lumps, which may reduce chlorination productivity.

The polyethylene may have a weight average molecular weight of about 150,000 g/mol to about 250,000 g/mol, or about 170,000 g/mol to about 220,000 g/mol, or about 180,000 g/mol to about 210,000 g/mol. This means that the molecular weight of polyethylene is high and the content of high molecular weight components is high, and as described above, it is possible to prevent a decrease in thermal stability due to low molecules in the chlorination process.

Additionally, the molecular weight distribution of the polyethylene may be from about 2 to about 10, or from about 3 to about 8, or from about 4 to about 6. This means that the molecular weight distribution of polyethylene is narrow. If the molecular weight distribution is wide, the difference in molecular weight between polyethylenes is large, so the chlorine content between polyethylenes may vary after the chlorination reaction, making uniform distribution of chlorine difficult. In addition, when low molecular weight components are melted, they have high fluidity and can block the pores of polyethylene particles, reducing chlorination productivity. However, in the present invention, since the molecular weight distribution is as described above, the difference in molecular weight between polyethylene after the chlorination reaction is not large, so chlorine can be substituted uniformly.

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

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

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

The method for producing polyethylene according to the present invention includes at least one first metallocene compound represented by the following formula (1); and polymerizing ethylene in the presence of at least one second metallocene compound selected from the compounds represented by the following formula (2), wherein the molar ratio of the first metallocene compound and the second metallocene compound is: It is 2.5:10 to 7:10.

[Formula 1]

In Formula 1,

Any one or more of R ₁ to R ₈ is -(CH ₂ ) _n -OR, where R is straight or branched chain alkyl of C _1-6 , n is an integer of 2 to 4,

The remainder of R ₁ to R ₈ are the same or different from each other, and are each independently hydrogen, halogen, C _1-20 straight or branched alkyl, C _2-20 straight or branched alkenyl, C _6-20 aryl. , C _7-40 alkylaryl, or C _7-40 arylalkyl, or two or more adjacent R ₁ to R ₄ or two or more adjacent R ₅ to R ₈ are connected to each other to form C It may form a substituted or unsubstituted C _6-20 aliphatic or aromatic ring with a _1-10 hydrocarbyl group,

Q ₁ and Q ₂ are the same or different from each other, and are each independently hydrogen, halogen, C _1-20 straight or branched alkyl, C _2-20 straight or branched alkenyl, C _2-20 straight or branched chain. alkoxyalkyl, C _6-20 aryl, C _7-40 alkylaryl, or 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 _ _} group, C _1-20 alkylsilyl, C _1-20 straight or branched alkoxy, or C _1-20 sulfonate group;

m is an integer of 0 or 1,

[Formula 2]

In Formula 2,

A ₂ is C _4-20 alkylene, C _4-20 alkenylene, C _6-20 arylene, C _4-20 cycloalkylene, C _7-22 aryl ( aryl) alkylene (akylene), or C _5-22 cycloalkyl alkylene,

R ₉ , R ₁₀ , R ₁₅ , and R ₁₆ are the same or different from each other, and are each independently hydrogen, halogen, C _1-20 straight or branched alkyl, C _2-20 straight or branched alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 straight or branched alkoxy, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 It is arylalkyl,

R ₁₁ to R ₁₄ and R ₁₇ to R ₂₀ are the same as or different from each other, and are each independently hydrogen, halogen, C _1-20 straight or branched alkyl, C _2-20 straight or branched alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 straight or branched alkoxy, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 It is arylalkyl, or two or more adjacent R ₁₁ to R ₁₄ or two or more adjacent R ₁₇ to R ₂₀ are connected to each other to form a substituted or unsubstituted C _6-20 aliphatic or aromatic ring. can form,

M ₂ is a group 4 transition metal,

_{X 3 and _ _ _ 1-20} alkoxy, or C _1-20 sulfonate group.

The substituents are described in more detail as follows.

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

The C _1-20 alkyl includes straight-chain, branched-chain, or cyclic alkyl. Specifically, C _1-20 alkyl includes C _1-20 straight-chain alkyl; C _1-15 straight chain alkyl; C _1-5 straight chain alkyl; C _3-20 branched or cyclic alkyl; C _4-20 branched or cyclic alkyl; C _4-15 branched or cyclic alkyl; Or it may be C _4-10 branched chain or cyclic alkyl. For example, the C _1-20 alkyl is methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, Cyclooctyl, etc. may be mentioned, but it is not limited thereto.

The C _2-20 alkenyl includes straight-chain or branched-chain alkenyl, and specifically includes allyl, ethenyl, propenyl, butenyl, pentenyl, and hexenyl, but is not limited thereto. no.

The C _6-20 aryl includes monocyclic or condensed aryl, and specifically includes phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, etc., but is not limited thereto.

The C _5-20 heteroaryl includes monocyclic or condensed heteroaryl, carbazolyl, pyridyl, quinoline, isoquinoline, thiophenyl, furanyl, imidazole, oxazolyl, thiazolyl, triazine, tetra Hydropyranyl, tetrahydrofuranyl, etc. may be mentioned, but it is not limited thereto.

Examples of the C _1-20 alkoxy include methoxy, ethoxy, phenyloxy, and cyclohexyloxy, but are not limited thereto.

The C _1-20 alkylsilyl or C _1-20 alkoxysilyl is a functional group in which 1 to 3 hydrogens of -SiH ₃ are replaced with 1 to 3 alkyl or alkoxy as described above, specifically methylsilyl, dimethyl. Alkylsilyl such as silyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl, or dimethylpropylsilyl; Alkoxysilyl such as methoxysilyl, dimethoxysilyl, trimethoxysilyl, or dimethoxyethoxysilyl; Alkoxyalkylsilyl such as methoxydimethylsilyl, diethoxymethylsilyl, or dimethoxypropylsilyl may be included, but is not limited thereto.

The silylalkyl of C _1-20 is a functional group in which one or more hydrogens of the alkyl described above are substituted with silyl, alkylsilyl, or alkoxysilyl, specifically -CH ₂ -SiH ₃ , methylsilylmethyl, trimethylsilylmethyl, or Dimethylethoxysilylpropyl, etc. may be mentioned, but it is not limited thereto.

The alkylene of C _1-20 is the same as the alkyl described above except that it is a divalent substituent, and specifically includes methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and cyclopropylene. , cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, etc., but is not limited thereto.

The C _2-20 alkenylene is the same as the alkenyl described above except that it is a divalent substituent, and specifically includes allylene, ethenylene, propenylene, butenylene, and pentenylene. It is not limited.

The C _6-20 arylene is the same as the aryl described above except that it is a divalent substituent, and specifically includes phenylene, biphenylene, naphthylene, anthracenylene, phenanthrenylene, fluorenylene, etc. However, it is not limited to this.

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

Specifically, in Formula 1, Q ₁ and Q ₂ may each be C _1-3 alkyl, preferably Q ₁ and Q ₂ are the same, and both Q ₁ and Q ₂ may be methyl.

Specifically, in Formula 1, X ₁ and X ₂ may each be halogen, and preferably chloro.

Specifically, in Formula 1, A ₁ may be silicon (Si).

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

Specifically, in Formula 1, R ₃ and R ₆ are the same or different from each other, and may each be unsubstituted C _1-6 alkyl or C _2-6 alkyl with C _1-6 alkoxy substituted, preferably At least one of R ₃ and R ₆ may be C _2-6 alkyl substituted with C _1-6 alkoxy. For example, R ₃ and R ₆ may each be methyl, n-butyl, n-pentyl, or tert-butoxy hexyl.

Additionally, in Formula 1, R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , and R ₈ are the same or different from each other and may each be hydrogen or C _1-3 alkyl, preferably hydrogen or methylyl. You can.

Meanwhile, the first metallocene compound may be represented by any one of the following formulas 1-1 to 1-6.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6, 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 They are the same as or different from each other, and each independently is a C _1-10 hydrocarbyl group.

Specifically, in Formulas 1-1 to 1-6, R' and R" may be hydrogen or C _1-6 alkyl, and preferably may be hydrogen.

Meanwhile, 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.

.

.

The first metallocene compound represented by Chemical Formula 1 or Chemical Formula 1-1, 1-2, 1-3, 1-4, 1-5, or 1-6 as described above is synthesized by applying known reactions. It may be possible, and for more detailed synthesis methods, refer to the examples.

On the other hand, the method for producing polyethylene according to the present invention is the first method represented by Formula 1 as described above or Formula 1-1, 1-2, 1-3, 1-4, 1-5, or 1-6. By using one or more metallocene compounds together with one or more second metallocene compounds described later, the melt index and density of polyethylene are optimized, while the complex viscosity is maximized in the low frequency region and the complex viscosity is increased in the high frequency region. By maintaining the optimal range, high productivity in the CPE process described later and excellent processability during extrusion can be secured.

In particular, the second metallocene compound represented by Formula 2 in the present invention has the characteristic of improving stability against heat by increasing molecular entanglement by increasing the middle molecular region in the polyethylene molecular structure. In particular, the second metallocene compound has a structure in which a transition metal coordinates between two indene derivatives and A ₂ of a specific structure connects the two indene derivatives. In this way, the second metallocene compound has a structure in which an indene derivative with relatively small steric hindrance is connected through A ₂ of the specific structure described above, so that a monomer such as ethylene can approach the central metal of the transition metal compound. It is easy to achieve higher polymerization activity, and has low hydrogen reactivity, so even when melt index (MI) and melt flow rate (MFRR) are adjusted by adding hydrogen, medium molecular weight olefin polymer is produced without deterioration in reaction activity. can do.

Specifically, in Formula 2, A ₂ may be C _6-20 arylene or C _6-12 arylene, or C _8-22 aryl dialkylene or C _8-14 aryl dialkylene. For example, it may be phenylene or naphthylene, phenyl dimethylene or naphthyl dimethylene, phenyl diethylene or naphthyl diethylene, and preferably phenylene or naphthyl dimethylene.

Specifically, in Formula 2, X ₃ and X ₄ may each be halogen, and more specifically, may be chloro.

Specifically, in Formula 2, M ₂ may be zirconium (Zr) or hafnium (Hf), and preferably may be zirconium (Zr).

Specifically, in Formula 2, R ₉ and R ₁₅ may each be hydrogen, halogen, C _1-20 straight-chain or branched alkyl, or each may be hydrogen, or C _1-6 straight-chain or branched alkyl. More specifically, R ₉ and R ₁₅ may be the same as each other, and may preferably be hydrogen.

Specifically, R ₁₀ to R ₁₆ may each be C _1-20 alkylsilyl, or C _1-20 silylalkyl, or each may be C _1-6 alkylsilyl, or C _1-6 silylalkyl. More specifically, R ₁₀ to R ₁₆ are the same as each other, and are preferably trimethylsilylmethyl.

Specifically, in Formula 2, R ₁₁ to R ₁₄ and R ₁₇ to R ₂₀ are each hydrogen, halogen, C _1-20 straight-chain or branched alkyl, or each is hydrogen, halogen, C _1-12 or C ₁ It may be _-6 linear or branched alkyl. Alternatively, two or more adjacent R ₁₁ to R ₁₄ or two or more adjacent R ₁₇ to R ₂₀ may be connected to form a C _6-20 aliphatic or aromatic ring. More specifically, R ₁₁ to R ₁₄ and R ₁₇ to R ₂₀ are the same as each other, and preferably are hydrogen.

Meanwhile, the second metallocene compound may be represented by the following formula 2-1 or 2-2.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2,

M ₂ , X ₃ , X ₄ , R ₁₀ , and R ₁₆ are as defined in Formula 2 above,

Ar are the same or different from each other, and are each independently C _6-20 arylene,

L ₁ and L ₂ are the same as or different from each other, and are each independently C _1-4 alkylene.

Specifically, in Formulas 2-1 and 2-2, Ar may each be C _6-12 arylene, and more specifically, may be phenylene or naphthylene.

Specifically, in Formulas 2-1 and 2-2, L ₁ and L ₂ may each be C _1-2 alkylene. More specifically, L ₁ and L ₂ are the same as each other and may be methylene or ethylene, preferably methylene.

Meanwhile, 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 Chemical Formula 2, Chemical Formula 2-1, or 2-2 as described above can be synthesized by applying known reactions, and the Examples can be referred to for more detailed synthesis methods.

Meanwhile, in this specification, equivalent weight (eq.) means molar equivalent.

Polyethylene according to the present invention includes at least one first metallocene compound represented by the above formula (1); It is prepared by polymerizing ethylene in the presence of at least one second metallocene compound selected from the compounds represented by Formula 2 above.

In particular, the molar ratio of the first metallocene compound and the second metallocene compound (first metallocene compound: second metallocene compound) is about 2.5:10 to about 7:10, specifically about It may be 3:10 to about 6:10, or about 4:10 to about 5:10. The molar ratio of the catalyst precursor may be in the range described above in terms of increasing the content of middle molecules and minimizing low molecular weight so as to produce chlorinated polyethylene with excellent chlorination productivity and thermal stability. In particular, when the molar ratio of the first metallocene compound and the second metallocene compound is applied in the above-described range, the amount of hydrogen input in the polymerization process can be applied at about 35 ppm to about 200 ppm compared to ethylene, wax ( Wax) content can be kept as low as 10% or less. The wax content can be measured by the volume ratio occupied by wax by separating the polymerization product using a centrifugal separation device, sampling 100 mL of the remaining hexane solvent, and settling for 2 hours.

Meanwhile, the metallocene catalyst used in the production of polyethylene in the present invention may be one in which the above-described first metallocene compound and the second metallocene compound are supported on a carrier, and in some cases, the carrier together with a co-catalyst compound. It may be contained in .

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

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

Specifically, the cocatalyst may be one or more selected from the group consisting of compounds represented by the following formulas 3 to 5:

[Formula 3]

-[Al(R ₃₁ )-O] _c -

In Formula 3 above,

R ₃₁ is each independently halogen, C _1-20 alkyl, or C _1-20 haloalkyl,

c is an integer greater than or equal to 2,

[Formula 4]

D(R ₄₁ ) ₃

In Formula 4 above,

D is aluminum or boron,

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

[Formula 5]

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

In Formula 5 above,

L is a neutral or cationic Lewis base,

[LH] ⁺ is Bronsted acid,

Q is Br ³⁺ or Al ³⁺ ,

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

The compound represented by Formula 3 may be, for example, an alkyl aluminoxane such as modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, etc.

The alkyl metal compound represented by the formula 4 is, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloroaluminum, dimethyl isobutyl aluminum, dimethyl ethyl aluminum, diethyl chloro. Aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl It may be aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc.

Compounds represented by Formula 5 include, for example, triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (p- Tolyl) boron, tripropylammonium tetra(p-tolyl) boron, triethylammonium tetra(o,p-dimethylphenyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenyl boron, N, N-dimethylanilinium tetraphenyl boron, N, N -Diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenyl Boron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra( p-tolyl) aluminum, triethylammonium tetra(o,p-dimethylphenyl) aluminum, tributylammonium tetra(p-trifluoromethylphenyl) aluminum, trimethylammonium tetra(p-trifluoromethylphenyl) aluminum, Tributylammonium Tetrapentafluorophenyl Aluminum, N,N-Dimethylanilinium Tetraphenyl Aluminum, N,N-Diethylanilinium Tetraphenyl Aluminum, N,N-Diethylanilinium Tetrapentafluorophenyl Aluminum, diethylammonium tetrapentafluorophenyl aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triphenylcarboniumtetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenylcarbonium It may be umtetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenyl boron, etc.

The amount of this co-catalyst supported may be about 5 mmol to about 20 mmol based on 1 g of carrier.

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

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

The drying temperature of the carrier is preferably about 200 ^o C to about 800 ^o C, more preferably about 300 ^o C to about 600 ^o C, and most preferably about 300 ^o C to about 400 ^o C. If the drying temperature of the carrier is less than about 200 ^o C, there is too much moisture, so the moisture on the surface reacts with the cocatalyst, and if it exceeds about 800 ^o C, the pores on the surface of the carrier merge, reducing the surface area, and also causing This is undesirable because many of the hydroxy groups are removed and only siloxane groups remain, thereby reducing the number of reaction sites with the cocatalyst.

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

If the amount of the hydroxy group is less than about 0.1 mmol/g, there are few reaction sites with the cocatalyst, and if it exceeds about 10 mmol/g, it may be caused by moisture other than the hydroxy 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 contained in the metallocene catalyst to the carrier may be 1:10 to 1:1000. When the carrier and metallocene compound are included in the above mass ratio, the optimal shape can be exhibited. Additionally, the mass ratio of co-catalyst compound to carrier may be 1:1 to 1:100.

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

In particular, the polyethylene according to the present invention includes at least one first metallocene compound represented by the above formula (1); It can be prepared by homopolymerizing ethylene in the presence of at least one second metallocene compound selected from the compounds represented by Formula 2 above.

Specifically, the polymerization temperature may be about 25 ^o C to about 500 ^o C, preferably about 60 ^o C to about 200 ^o C, and more preferably about 70 ^o C to about 100 ^o C. Additionally, the polymerization pressure is from about 1 kgf/cm ² to about 100 kgf/cm ² , preferably from about 3 kgf/cm ² to about 50 kgf/cm ² , and more preferably from about 5 kgf/cm ² to about 20 kgf. It can be / ^cm2 .

Additionally, the polymerization reaction can be performed under conditions where hydrogen gas is supplied.

At this time, the hydrogen gas activates the inactive site of the metallocene catalyst and causes a chain transfer reaction to control the molecular weight. The metallocene compound of the present invention has excellent hydrogen reactivity, and therefore, by controlling the amount of hydrogen gas used during the polymerization process, polyethylene having a desired level of melt index, density, and complex viscosity range can be effectively obtained.

The hydrogen gas may be added in an amount of about 35 ppm to about 200 ppm, or about 40 ppm to about 180 ppm, or about 50 ppm to about 150 ppm, based on the total weight of ethylene. By adjusting the amount of hydrogen gas used within the above range, the melt index, density, and complex viscosity of the polyethylene produced can be adjusted within the desired range while exhibiting sufficient catalytic activity. Accordingly, polyethylene with appropriate physical properties depending on the application can be manufactured. there is. More specifically, in the catalyst system using the specific first and second metallocene compounds as described above, when the amount of hydrogen input is less than about 35 ppm compared to ethylene, the melt index MI of polyethylene is lowered and the complex The viscosity increases, and as a result, the pattern viscosity (MV) increases after the chlorination process, which may result in increased processing load during subsequent compound processing and an uneven surface. On the other hand, if the amount of hydrogen input exceeds about 200 ppm compared to ethylene, the complex viscosity of polyethylene decreases because a large amount of low molecular weight is generated, and the change in particle shape increases during chlorination processing, which reduces productivity and crosslinking degree. The tensile strength may decrease.

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

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

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

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

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

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

The chlorination reaction is preferably performed 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 Preferred is 10 hours, or about 1 hour to about 9 hours, or about 2 hours to about 8 hours.

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

The chlorinated polyethylene increases the content of the high-molecular region in the molecular structure and minimizes the content of the low-molecular region, improving heat stability during chlorination processing, for example, in a slurry (water or HCl aqueous solution) at about 60 ^o C. After being prepared by reacting chlorine under conditions of about 150 ^o C, the mooney viscosity (MV, Mooney viscosity) measured under conditions of 121 ^o C may be from 70 to 120, or from 80 to 110, or from 90 to 100. . Here, the unit of pattern viscosity is a pattern unit (MU, Mooney unit), which is usually not indicated as a separate unit, but if conversion is necessary, 1 pattern unit (MU, Mooney unit) can be said to be 0.083 Nm.

On the other hand, if the pattern viscosity of the chlorinated polyethylene is less than about 60, the tensile strength of wires and cables made from the chlorinated polyethylene compound may decrease. In addition, when the pattern viscosity of the chlorinated polyethylene exceeds about 85, as will be described later, when processing CPE compounds for wires and cables through compounding with inorganic additives and crosslinking agents, the surface is not smooth and rough, It may lose its luster and cause problems with its appearance.

Specifically, the Mooney viscosity (MV) ranges from about 75 ^o C to about 85 o C to about 120 ^o C to about 140 ^o C when about 500 kg to about 600 kg of polyethylene is used as a slurry ⁽ water or HCl aqueous solution). After increasing the temperature at a rate of about 15 ^o C/hr to about 18.5 ^o C/hr to a final temperature of about 120 ^o C to about 140 o C, chlorination with gaseous chlorine for about 2 hours to about 5 hours at a final temperature of about 120 o C to about 140 ^o C. It may be a value measured for chlorinated polyethylene obtained by performing the reaction. At this time, the chlorination reaction can be performed by injecting gaseous chlorine while raising the temperature and maintaining the pressure in the reactor at about 0.2 MPa to about 0.4 MPa, and the total amount of chlorine added is about 650 kg to about 750 kg. there is.

In addition, the method for measuring the Mooney viscosity (MV), tensile strength, and tensile elongation of the chlorinated polyethylene is as described in Test Example 2, which will be described later, and the specific measurement method is omitted. .

For example, the chlorinated polyethylene may have a chlorine content of about 20% by weight to about 50% by weight, about 31% by weight to about 45% by weight, or about 35% by weight to about 40% by weight. Here, the chlorine content of the chlorinated polyethylene can be measured using combustion ion chromatography (Combustion IC, Ion Chromatography) analysis. As an example, the combustion ion chromatography analysis method uses a combustion IC (ICS-5000/AQF-2100H) device equipped with an IonPac AS18 (4 x 250 mm) column, with an internal device temperature (Inlet temperature) of 900 ^o C and an external 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 device conditions and measurement conditions for measuring the chlorine content are the same as those described in Test Example 2, which will be described later, and detailed descriptions will be omitted.

Specifically, the chlorinated polyethylene according to the present invention may have a Mooney viscosity (MV) of about 90 to about 100 as described above under the condition that the chlorine content is 35% by weight to 40% by weight.

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

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

Meanwhile, according to another embodiment of the invention, a PVC composition containing chlorinated polyethylene and vinyl chloride polymer (PVC) as described above is provided.

For example, the PVC composition may include about 5% to about 20% by weight of chlorinated polyethylene and about 50% to about 95% by weight of polyvinyl chloride (PVC) as described above.

For example, the chlorinated polyethylene may be about 5% by weight to about 20% by weight, or about 5% by weight to about 10% by weight.

For example, the vinyl chloride polymer (PVC) may be about 50% by weight to about 95% by weight, or about 60% by weight to about 90% by weight.

As an example, the PVC composition contains 5 to about 600 parts by weight of an inorganic additive solution such as TiO ₂ , CaCO ₃ , complex stearate (Ca, Zn-stearate), or about 600 parts by weight based on 100 parts by weight of chlorinated polyethylene as described above. It may additionally include about 10 parts by weight to about 200 parts by weight.

As a specific example, the PVC composition includes about 5% to about 20% by weight of chlorinated polyethylene, about 60% to about 90% by weight of vinyl chloride polymer (PVC), and about 1% to about 10% by weight of TiO ₂ as described above. Weight%, it may include about 1% by weight to about 10% by weight of CaCO ₃ and about 1% by weight to about 10% by weight of complex stearate (Ca, Zn-stearate).

For example, the PVC composition may have a plasticization time of about 170 seconds or less, about 150 seconds or less, or about 150 seconds to about 100 seconds. In addition, when the PVC composition is mixed with vinyl chloride polymer (PVC) under conditions of, for example, 160 ^o C to 190 ^o C, the Charpy impact strength measured under room temperature conditions using the ASTM E 23 method is 24 kJ/㎡ or more. You can. Within this range, excellent physical property balance and productivity are achieved. The method for measuring the Charpy impact strength of the PVC composition is as described in Test Example 3 described later, and the specific measurement method is omitted.

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

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

[Manufacture of catalyst precursor]

Synthesis Example 1: Preparation of the first metallocene compound

1-1 Preparation of ligand compounds

Add 10.8 g (100 mmol) of chlorobutanol to a dried 250 mL Schlenk flask, then add 10 g of molecular sieve and 100 mL of methyl tert-butyl ether. -butyl ether, MTBE) was added, and then 20 g of sulfuric acid was slowly added over 30 minutes. The reaction mixture slowly turned pink over time, and after 16 hours, it was poured into an ice-cold saturated sodium bicarbonate solution. Diethyl ether (Ether, 100 _mL -Butoxy)-4-chlorobutane [1-(tert butoxy)-4-chlorobutane] 10 g (60% yield) was obtained.

¹ H NMR (500 MHz, CDCl ₃ , ppm): δ 1.16 (9H, s), 1.67 - 1.76 (2H, m), 1.86 - 1.90 (2H, m), 1.94 (1H, m), 3.36 (2H, m), 3.44 (1H, m), 3.57 (3H, m).

4.5 g (25 mmol) of 1-(tertiary-butoxy)-4-chlorobutane synthesized above was added to a dried 250 mL Shrink flask and dissolved in 40 mL of tetrahydrofuran (THF). 20 mL of sodium cyclopentadienylide THF solution was slowly added thereto and stirred for one day. This reaction mixture was quenched by adding 50 mL of water, extracted with diethyl ether (50 mL x 3), and the collected organic layer was thoroughly washed with brine. The remaining moisture was dried with MgSO ₄ and filtered, and the solvent was removed under reduced pressure to quantify the dark brown, viscous product, 2-(4-(tert-butoxy)butyl) cyclopenta-1,3-diene. It was obtained in good yield.

¹ H NMR (500 MHz, CDCl ₃ , ppm): δ 1.16 (9H, s), 1.54 - 1.60 (4H, m), 1.65 (1H, m), 1.82 (1H, m), 2.37 - 2.42 (2H, m), 2.87, 2.92 (2H, s), 3.36 (2H, m), 5.99 (0.5H, s), 6.17 (0.5H, s), 6.25 (0.5H, s), 6.34 (0.5H, s) , 6.42 (1H, s).

1-2 Preparation of transition metal compounds

4.3 g (23 mmol) of the ligand compound synthesized in 1-1 was added to a dried 250 mL Shrink flask and dissolved in 60 mL of tetrahydrofuran (THF). 11 mL of n-butyllithium (n-BuLi, 2.0 M hexane solution, 28 mmol) was added thereto and stirred for one day. Then, 3.83 g (10.3 mmol) of ZrCl ₄ (THF) ₂ was added to this solution in 50 mL of diluted solution. It was slowly added to the flask dispersed in ethyl ether at -78 ^o C (Celsius degree).

When this reaction mixture was raised to room temperature (rt, 25 ^o C), it changed from a light brown suspension to a cloudy yellow suspension. After stirring for a day, all solvents in the reaction mixture were dried, 200 mL of hexane was added and sonication was used to settle the mixture, and the hexane solution floating on the upper layer was collected by decantation using a cannula. The hexane solution obtained by repeating this process twice was dried under reduced pressure in vacuum to produce bis(3-(4-(tertiary-butoxy)butyl-2,4-dienyl)zirconium(IV), a compound in the form of a pale yellow solid. It was confirmed that chloride [bis(3-(4-(tert-butoxy)butyl-2,4-dien-yl) zirconium(IV) chloride] was produced.

¹ H NMR (500 MHz, CDCl ₃ , ppm): δ 0.84 (6H, m), 1.14 (18H, s), 1.55 - 1.61 (8H, m), 2.61 (4H, m), 3.38 (4H, m) , 6.22 (3H, s), 6.28 (3H, s).

Synthesis Example 2: Preparation of the first metallocene compound

2-1 Preparation of ligand compounds

6.0 mL (40 mmol) of tetramethylcyclopentadiene (TMCP) was dissolved in THF (60 mL) in a dried 250 mL Shrink flask, and then cooled to -78°C. 17 mL (42 mmol) of n-BuLi 2.5 M hexane solution was slowly added dropwise and stirred at room temperature overnight. In a separate 250 mL Shrink flask, 4.8 mL (40 mmol) of dichlorodimethylsilane was dissolved in n-hexane, cooled to -78°C, and the previously reacted TMCP-lithiation solution was slowly injected. This was stirred at room temperature overnight, and the solvent was removed under reduced pressure. After the reaction, the product obtained was dissolved in toluene and filtered to remove the remaining LiCl to obtain 7.0 g (33 mmol) of chloromethyl (tetramethylcyclopentadienyl) silane (CDMTS) in the form of a yellow liquid (yield 83). %).

¹ H NMR (500 MHz, CDCl ₃ , ppm): δ 0.24 (6H, s), 1.82 (6H, s), 1.98 (6H, s), 3.08 (1H, s).

2.72 g of 3-(6-(tert-butoxy)hexyl)-1H-indene, T-Ind) in a dried 250 mL Shrink flask. (10 mmol) was dissolved in 50 mL of THF, and then 8.2 mL (20.4 mmol) of n-BuLi 2.5 M hexane solution was slowly added dropwise in a dry ice/acetone bath. After reaction overnight at room temperature, a red solution was obtained. In a separate 250 mL Shrink flask, 2.15 g (10 mmol) of chloromethyl(tetramethylcyclopentadienyl)silane (CDMTS) synthesized previously was dissolved in THF, and then the previously prepared (T-Ind)-lithiation solution ( T-Ind-Li solution) was added dropwise in a dry ice/acetone bath. After reaction overnight at room temperature, a dark brown slurry was observed. Quenched with water and extracted with diethyl ether to obtain 4.18 g (9.27 mmol) (yield 92.7%).

¹ H NMR (500 MHz, CDCl ₃ , ppm): δ 0.43 (3H, s), -0.15 (3H, s), 1.21 (9H, s), 1.42-2.08 (22H, m), 2.61 (1H, s) ), 3.35-3.38 (2H, m), 3.52 (1H, s), 6.21 (1H, s), 7.17-7.43 (4H, m).

2-2 Preparation of metallocene compounds

Dissolve 4.18 g (9.27 mmol) of the ligand compound synthesized in 2-1 above in 100 mL of toluene, add 4.4 mL (4 equivalents) of MTBE, and add 8.2 mL of n-BuLi 2.5M hexane solution and 20.4 mmol on dry ice. /It was added dropwise to an acetone bath. After reaction overnight at room temperature, a reddish slurry was obtained. In a glove box, 3.50 g (9.27 mmol) of ZrCl ₄ (THF) ₂ was prepared to make a 50 mL toluene solution, and the ligand-lithiation solution (ligand-Li solution) was added dropwise in a dry ice/acetone bath. After reaction overnight at room temperature, a reddish slurry was observed. The reaction product was filtered to remove LiCl, then about 90% of toluene was removed by vacuum drying, and then recrystallized from hexane. The slurry was filtered to obtain 2.5 g (4.1 mmol) of yellow filter cake (yield 44.1%).

¹ H NMR (500 MHz, CDCl ₃ , ppm): δ 0.93 (3H, s), 1.17 (12H, s), 1.37-1.63 (8H, m), 2.81-2.87 (1H, m), 2.93-2.97 ( 1H, m), 3.29-3.31 (2H, t), 5.55 (1H, s), 7.02-7.57 (4H, m).

Comparative Synthesis Example 1: Preparation of the first metallocene compound

t-butyl-O-(CH ₂ ) 6 -Cl was prepared using _6- chlorohexanol by the method described in Tetrahedron Lett. 2951 (1988), and cyclopentadienyl sodium (NaCp) was added to it. By reaction, t-butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80 ^o C/0.1 mmHg).

Additionally, t-butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 ^o C, n-BuLi was slowly added, the temperature was raised to room temperature, and reaction was performed for 8 hours. The synthesized lithium salt solution was slowly added to the suspension solution of ZrCl ₄ (THF) ₂ (170 g, 4.50 mmol)/THF (30 mL) at -78 ^o C and reacted at room temperature for another 6 hours. I ordered it. All volatile substances 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 precipitate at low temperature (-20 ^o C). The obtained precipitate was filtered at low temperature to obtain [tBu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ ] in the form of a white solid (92% yield).

¹ H-NMR (300 MHz, CDCl ₃ , ppm): δ 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 (300 MHz, CDCl ₃ , ppm): δ 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.31, 30.14, 29.18, 27.58, 26.00.

Synthesis Example 3: Preparation of second metallocene compound

1,8-bis(bromomethyl)naphthalene [6.3 g (20 mmol) of 1,8-bis(bromomethyl)naphthalene and 8.3 g (40 mmol) of methyl TMS-Indene Lithium salt, respectively. After dissolving in 80 mL of THF, it was added dropwise in a dry ice/acetone bath and stirred at room temperature overnight. After completion of the stirring, the reaction product was extracted with diethyl ether/water, the residual moisture in the organic layer was removed with MgSO ₄ , and the solvent was removed under vacuum and reduced pressure conditions to obtain a liquid ligand compound. 11.1 g (20 mmol, Mw 556.93) was obtained.

11 g of the obtained ligand compound was dissolved in a mixed solvent of 80 mL of toluene and 5 mL of methyl tert-butyl ether (MTBE), and 16.7 mL (41.6 mmol) of a 2.5 M hexane solution of n-butyl lithium was added. It was added dropwise and stirred at room temperature. Then, 7.5 g (19.8 mmol) of ZrCl ₄ (THF) ₂ was added to 80 mL of toluene to prepare a slurry, then transferred in a dry ice/acetone bath and stirred at room temperature overnight.

After the stirring was completed, the slurry was filtered to remove LiCl, and toluene in the filtrate was removed by vacuum drying, then 100 mL of hexane was added and sonication was performed for 1 hour. Afterwards, the slurry was filtered to obtain 4.5 g of a metallocene compound (yield 62.3 mol%, yellow solid) as a filtered solid.

¹ H NMR (500 MHz, CDCl ₃ , ppm): δ 8.16-6.95 (14H, m), 5.99 (2H, d), 3.99 (2H, m), 3.83 (2H, m), 3.39 (2H, m) , 0.15 (18H, d).

Comparative Synthesis Example 2: Preparation of a second metallocene compound

tBu-O-(CH ₂ ) ₆ )(CH ₃ )Si(C ₅ (CH ₃ ) ₄ )(tBu-N)TiCl ₂ manufacture of

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

After adding 500 g of trichloromethylsilane (MeSiCl ₃ ) and 1 L of THF to the reactor, the temperature of the reactor was cooled to -20 ^o C. 560 g of the synthesized 6-t-butoxyhexyl magnesium chloride was added to the reactor at a rate of 5 mL/min using a feeding pump. After the feeding of the Grignard reagent was completed, the reactor temperature was slowly raised to room temperature and stirred for 12 hours. It was confirmed that white MgCl ₂ salt was produced after 12 hours of reaction. 4 L of hexane was added and the salt was removed through labdori to obtain a filter solution. The obtained filter solution was added to the reactor and hexane was removed at 70 ^o C to obtain a pale yellow liquid. The obtained liquid was confirmed to be the desired methyl(6-t-butoxy hexyl)dichlorosilane {Methyl(6-t-butoxy hexyl)dichlorosilane} compound through 1H-NMR.

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

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

^TiCl ₃ (THF) ₃ (10 mmol) was added rapidly. The reaction solution was slowly raised from -78 ^o C to room temperature and stirred for 12 hours. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature and stirred for 12 hours. After stirring for 12 hours, a dark black solution with a blue tinge was obtained. After THF was removed from the resulting reaction solution, hexane was added and the product was filtered. After removing hexane from the ^resulting filter solution, the desired methyl (6-t-butoxyhexyl)silyl (η5-tetramethylcyclopentadienyl) (t-butylamido)] titanium dichloride ([methyl (6-t-buthoxyhexyl)silyl(η5-tetramethylCp)(t-Butylamido)]TiCl ₂ , (tBu-O-(CH ₂ ) ₆ )(CH ₃ )Si-(C ₅ (CH ₃ ) ₄ )(tBu -N)TiCl ₂ ) was confirmed.

¹ H-NMR (300 MHz, CDCl ₃ , ppm): δ 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 - 0.8 (m), 1.4 (s, 9H), 1.2(s, 9H), 0.7 (s, 3H).

[Manufacture of supported catalyst]

Preparation Example 1: Preparation of supported catalyst

5.0 kg of toluene solution was added to a 20 L stainless steel (sus) high pressure reactor, and the reactor temperature was maintained at 40 ^o C. 1 kg of silica (SP948, manufactured by Grace Davison) dehydrated by applying vacuum for 12 hours at a temperature of 600 ^o C was added to the reactor and the silica was sufficiently dispersed, and then 109.75 g of the metallocene compound of Synthesis Example 1 was added to toluene. It was dissolved, added, and stirred at 40 ^o C at 200 rpm for 2 hours to react. Afterwards, stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decantated.

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

3.0 kg of toluene was added to the reactor, and 358.58 g of the metallocene compound of Synthesis Example 3 was dissolved in 1 L of toluene solution and added to the reactor, and stirred at 40 ^o C and 200 rpm for 2 hours to react. At this time, the ratio between the metallocene compound of Synthesis Example 1 and the metallocene compound of Synthesis Example 3 was 4:10 based on the molar ratio. After lowering the reactor temperature to room temperature, stirring was stopped, settling was performed for 30 minutes, and the reaction solution was decantated.

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

3.0 kg of hexane was added to the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. 910 g-SiO ₂ hybrid supported catalyst was prepared by drying under reduced pressure at 40 ^o C for 4 hours.

Preparation Example 2: Preparation of supported catalyst

A hybrid supported catalyst was prepared in the same manner as Preparation Example 1, except that the metallocene compound of Synthesis Example 1 and the metallocene compound of Synthesis Example 3 were added at a molar ratio of 5:10.

Preparation Example 3: Preparation of supported catalyst

A hybrid supported catalyst was prepared in the same manner as Preparation Example 1, except that the metallocene compound of Synthesis Example 2 and the metallocene compound of Synthesis Example 3 were added at a molar ratio of 5:10.

Comparative Preparation Example 1: Preparation of supported catalyst

Prepared in the same manner as Preparation Example 1, but using the metallocene compounds of Comparative Synthesis Examples 1 and 2 instead of the metallocene compounds of Synthesis Examples 1 and 2, and the metallocene compound of Comparative Synthesis Example 1. A hybrid supported catalyst was prepared by varying the ratio of 2 with the metallocene compound to 3:10 based on the molar ratio.

Comparative Preparation Example 2: Preparation of supported catalyst

A hybrid supported catalyst was prepared in the same manner as Comparative Preparation Example 1, except that the ratio between the metallocene compound of Comparative Synthesis Example 1 and the metallocene compound of Comparative Synthesis Example 2 was changed to 4:10 based on the molar ratio. .

Comparative Preparation Example 3: Preparation of supported catalyst

A hybrid supported catalyst was prepared in the same manner as Comparative Preparation Example 1, except that the ratio between the metallocene compound of Comparative Synthesis Example 1 and the metallocene compound of Comparative Synthesis Example 2 was changed to 5:8 based on the molar ratio. .

Comparative Preparation Example 4: Preparation of supported catalyst

A hybrid supported catalyst was prepared in the same manner as Preparation Example 1, except that the metallocene compound of Synthesis Example 1 and the metallocene compound of Synthesis Example 3 were added at a molar ratio of 2:10.

[Manufacture of polyethylene]

Example 1-1

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

First, hexane 25 ton/hr, ethylene 10 ton/hr, hydrogen 15 m ³ /hr, and triethylaluminum (TEAL) 10 kg/hr were respectively injected into a reactor with a capacity of 100 m ³ , and also in Preparation Example 1. The hybrid supported metallocene catalyst was injected at 0.5 kg/hr. Here, the input amount of hydrogen gas was 52 ppm based on ethylene content. Accordingly, the ethylene was continuously reacted in the form of a hexane slurry 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 went through a solvent removal and drying process to produce high-density polyethylene (HDPE, homopolymer) in powder form. PE) was prepared.

Example 1-2

Prepared in the same manner as Example 1-1, but using the supported catalyst prepared in Preparation Example 2 instead of the supported catalyst prepared in Preparation Example 1, and varying the amount of hydrogen input to 97 ppm, high density polyethylene in powder form was prepared. was manufactured.

Example 1-3

Prepared in the same manner as Example 1-1, but using the supported catalyst prepared in Preparation Example 2 instead of the supported catalyst prepared in Preparation Example 1, and varying the amount of hydrogen input to 144 ppm, high density polyethylene in powder form was prepared. was manufactured.

Example 1-4

Prepared in the same manner as Example 1-1, but using the supported catalyst prepared in Preparation Example 3 instead of the supported catalyst prepared in Preparation Example 1, and varying the amount of hydrogen input to 85 ppm, high density polyethylene in powder form was prepared. was manufactured.

Comparative Example 1-1

A commercially available high-density polyethylene (HDPE) product manufactured using Zeigier-Natta catalyst (Z/N-1) and having a melt index (MI ₅ , 190 ^o C, 5 kg) of 0.46 g/10 min (product name CE6040K) , manufactured by LG Chem) was prepared in Comparative Example 1-1.

Comparative Example 1-2

A commercially available high-density polyethylene (HDPE) product (product name CE6040X) manufactured using a Ziegier-Natta catalyst (Z/N-2) and having a melt index (MI ₅ , 190 ^o C, 5 kg) of 0.98 g/10 min. , manufacturer LG Chem) was prepared in Comparative Example 1-2.

Comparative Example 1-3

A commercially available high-density polyethylene (HDPE) product (product name CE2080) manufactured using Zeigier-Natta catalyst (Z/N-3) and having a melt index (MI ₅ , 190 ^o C, 5 kg) of 1.28 g/10 min. , manufactured by LG Chem) was prepared in Comparative Example 1-3.

Comparative Examples 1-4 and 1-5

Prepared in the same manner as Example 1-1, except that the supported catalysts prepared in Comparative Preparation Examples 1 and 2 were used instead of the supported catalysts prepared in Preparation Example 1, and the amount of hydrogen input was 3 ppm each based on the ethylene content. and 18 ppm, high density polyethylene in powder form was prepared.

Comparative Examples 1-6 and 1-7

Prepared in the same manner as Example 1-1, except that the supported catalyst prepared in Comparative Preparation Example 3 was used instead of the supported catalyst prepared in Preparation Example 1, and the amount of hydrogen input was 18 ppm and 3 ppm, respectively, based on ethylene content. In this way, high-density polyethylene in powder form was manufactured.

Comparative Example 1-8

Prepared in the same manner as Example 1-1, except that the supported catalyst prepared in Comparative Preparation Example 4 was used instead of the supported catalyst prepared in Preparation Example 1, and the amount of hydrogen input was changed to 30 ppm based on the ethylene content, High-density polyethylene in powder form was manufactured.

Test example 1

The physical properties of the polyethylene prepared in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-8 were measured by the following method, 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 at a temperature of 190 ^o C and load of 5 kg and 21.6 kg, respectively, using the method of ASTM D 1238, and was expressed as the weight (g) of the polymer melted for 10 minutes. .

2) Melt Flow Rate (MFRR)

The melt flow rate (MFRR, MI _21.6/5 ) was calculated 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 using the method of ASTM D 1238. .

3) Density

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

4) Complex viscosity measurement according to frequency

Each complex viscosity was measured at a frequency (ω) of 0.05 rad/s and a frequency (ω) of 500 rad/s using a rotational rheometer.

Specifically, complex viscosity was measured according to frequency: η*(ω0.05) and η*(ω500) using a rotational rheometer ARES (Advanced Rheometric Expansion System, ARES G2) from TA instruments. Samples were prepared at 190 ^o C using parallel plates with a diameter of 25.0 mm, with a gap of 2.0 mm. Measurements were made in dynamic strain frequency sweep mode, with a strain of 5% and a frequency of 0.05 rad/s to 500 rad/s, measuring a total of 41 points, 10 points for each decade. Among these, the complex viscosity measured at a frequency of 05 rad/s and a frequency (ω) of 500 rad/s is shown in Table 1 below.

catalyst Hydrogen input amount
(ppm) polymer MI ₅
(5 kg, 190 ^o C, g/10 min) MI _21.6 (21.6 kg, 190 ^o C, g/10 min) MFRR
(21.6/5) density
(g/ ^cm3 ) η*
(ω0.05, Pa·s) η*
(ω500, Pa·s) Example
1-1 Manufacturing example
One 52 HomoPE 0.21 2.84 13.52 0.950 113620 1480 Example 1-2 Manufacturing example
2 97 HomoPE 0.27 3.54 13.11 0.951 94970 1390 Example 1-3 Manufacturing example
2 144 Homo PE 0.35 5.32 15.20 0.950 79920 1070 Example 1-4 Manufacturing example
3 85 Homo PE 0.28 3.90 13.93 0.951 90540 1360 Comparative Example 1-1 Z/N-1 - Homo PE 0.46 4.74 10.30 0.951 65290 1410 Comparative Example 1-2 Z/N-2 - HomoPE 0.98 9.70 9.90 0.953 55140 1120 Comparative Example 1-3 Z/N-3 - HomoPE 1.28 19.33 15.10 0.958 39160 680 Comparative Example 1-4 comparison
Manufacturing example
One 3 HomoPE 0.63 6.68 10.60 0.951 61210 1410 Comparative Example 1-5 comparison
Manufacturing example
2 18 HomoPE 0.84 8.99 10.70 0.951 57890 1340 Comparative Example 1-6 comparison
Manufacturing example
3 18 Homo PE 1.60 13.44 8.40 0.951 28700 1075 Comparative Example 1-7 comparison
Manufacturing example
3 3 HomoPE 0.98 9.70 9.90 0.95 40980 1310 Comparative Example 1-8 comparison
Manufacturing example
4 30 HomoPE 0.18 2.14 11.89 0.951 134450 1800

As shown in Table 1, compared to the comparative examples, it can be confirmed that the melt index and density of the examples are optimized, and the complex viscosity is all implemented in the optimal range at frequencies of 0.05 rad/s and 500 rad/s. there was.

Test example 2

Using the polyethylene prepared in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-8, chlorinated polyethylene of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-8 below was manufactured.

[Manufacture of chlorinated polyethylene]

Add 5000 L of water and 550 kg of high-density polyethylene prepared in Example 1-1 to the reactor, then add sodium polymethacrylate as a dispersant, oxypropylene and oxyethylene copolyether as emulsifiers, and benzoyl peroxide as a catalyst. The temperature was increased from 80 ^o C to 132 ^o C at a rate of 17.3 ^o C/hr, and then chlorinated with gaseous chlorine at a final temperature of 132 ^o C for 3 hours. At this time, in the chlorination reaction, gaseous chlorine was injected at a temperature of 0.3 MPa at the same time as the temperature was raised, and the total amount of chlorine introduced was 700 kg. The chlorinated reactant was neutralized by adding NaOH for 4 hours, washed again with flowing water for 4 hours, and finally dried at 120 ^o C to prepare chlorinated polyethylene in powder form.

In addition, the polyethylene produced in Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-8 were also produced in powder form by the same method as above.

As described above, Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2 were prepared using the polyethylene prepared in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-8. The physical properties of -8 chlorinated polyethylene were measured in the following manner, and the results are shown in Table 2 below.

1) Mooney viscosity (MV) 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). Here, the unit of pattern viscosity is a pattern unit (MU, Mooney unit), which is usually not indicated as a separate unit, but if necessary, 1 pattern unit (MU, Mooney unit) can be converted to 0.083 Nm.

2) Drying time of CPE (min)

After preparing CPE by reacting chlorine in a slurry (water or HCl aqueous solution) under conditions of about 60 ^o C to about 150 ^o C, the produced CPE was added to NaOH to neutralize it for 4 hours, and then washed again with flowing water for 4 hours. After washing, it was finally dried at 120 ^o C to prepare the final chlorinated polyethylene product in powder form. Here, drying was carried out until the moisture content of the final product was 0.4 wt% or less, and the time taken was measured in minutes and expressed as drying time (min).

Example Comparative example 2-1 2-2 2-3 2-4 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 MV of CPE (121 ^o C, ML1+4) 100 95 90 95 100 90 70 100 95 90 95 125 Drying time (min) 115 125 155 140 200 220 270 200 205 320 250 115

As shown in Table 2, compared to the comparative example, the examples facilitate the deoxidation, dehydration, and drying processes during chlorination processing and enable an increase in the reaction temperature in the chlorination process, thereby leading to superior CPE productivity and pattern viscosity after chlorination. It can also be seen that the optimal range can be secured.

Claims (15)

The melt index MI ₅ (measured at 190 ^o C and load of 5 kg) is less than or equal to 0.55 g/10 min,
The melt index MI _21.6 (measured at 190 ^o C and a load of 21.6 kg) is less than or equal to 6 g/10 min,
The complex viscosity (η*(ω0.05), complex viscosity) measured at a frequency (ω) of 0.05 rad/s is more than 68000 Pa·s,
Complex viscosity (η*(ω500), complex viscosity) measured at a frequency (ω) of 500 rad/s is 900 Pa·s to 1600 Pa·s, and
which is an ethylene homopolymer,
polyethylene.
delete According to paragraph 1,
The polyethylene has a melt index MI ₅ (measured at 190 ^o C, 5 kg load) of 0.1 g/10min to 0.55 g/10min,
polyethylene.
According to paragraph 1,
The polyethylene has a melt index MI _21.6 (measured at 190 ^o C, 21.6 kg load) of 2.2 g/10min to 6 g/10min,
polyethylene.
According to paragraph 1,
The polyethylene has a melt flow index (MFRR _21.6/5 , the melt index measured at 190 ^o C and a load of 21.6 kg divided by the melt index measured at 190 ^o C and a load of 5 kg using the method of ASTM D 1238) of 10. to 18 people,
polyethylene.
According to paragraph 1,
The polyethylene has a complex viscosity (η*(ω0.05), complex viscosity) measured at a frequency (ω) of 0.05 rad/s of 68000 Pa·s to 180000 Pa·s,
polyethylene.
According to paragraph 1,
The polyethylene has a density of 0.947 g/cm ³ or more,
polyethylene.
At least one first metallocene compound represented by the following formula (1); And homopolymerizing ethylene in the presence of at least one second metallocene compound selected from the compounds represented by the following formula (2),
The molar ratio of the first metallocene compound and the second metallocene compound is 2.5:10 to 7:10,
Method for producing polyethylene according to any one of claims 1 and 3 to 7:
[Formula 1]

In Formula 1,
Any one or more of R ₁ to R ₈ is -(CH ₂ ) _n -OR, where R is straight or branched chain alkyl of C _1-6 , n is an integer of 2 to 4,
The remainder of R ₁ to R ₈ are the same or different from each other, and are each independently hydrogen, halogen, C _1-20 straight or branched alkyl, C _2-20 straight or branched alkenyl, C _6-20 aryl. , C _7-40 alkylaryl, or C _7-40 arylalkyl, or two or more adjacent R ₁ to R ₄ or two or more adjacent R ₅ to R ₈ are connected to each other to form C It may form a substituted or unsubstituted C _6-20 aliphatic or aromatic ring with a _1-10 hydrocarbyl group,
Q ₁ and Q ₂ are the same or different from each other, and are each independently hydrogen, halogen, C _1-20 straight or branched alkyl, C _2-20 straight or branched alkenyl, C _2-20 straight or branched chain. alkoxyalkyl, C _6-20 aryl, C _7-40 alkylaryl, or 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 _ _} group, C _1-20 alkylsilyl, C _1-20 straight or branched alkoxy, or C _1-20 sulfonate group;
m is an integer of 0 or 1,
[Formula 2]

In Formula 2,
A ₂ is C _4-20 alkylene, C _4-20 alkenylene, C _6-20 arylene, C _4-20 cycloalkylene, C _7-22 arylalkylene, or C _5-22 cycloalkylalkylene; ,
R ₉ , R ₁₀ , R ₁₅ , and R ₁₆ are the same or different from each other, and are each independently hydrogen, halogen, C _1-20 straight or branched alkyl, C _2-20 straight or branched alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 straight or branched alkoxy, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 It is arylalkyl,
R ₁₁ to R ₁₄ and R ₁₇ to R ₂₀ are the same as or different from each other, and are each independently hydrogen, halogen, C _1-20 straight or branched alkyl, C _2-20 straight or branched alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 straight or branched alkoxy, C _6-20 aryl, C _7-40 alkylaryl, or C _7-40 It is arylalkyl, or two or more adjacent R ₁₁ to R ₁₄ or two or more adjacent R ₁₇ to R ₂₀ are connected to each other to form a substituted or unsubstituted C _6-20 aliphatic or aromatic ring. can form,
M ₂ is a group 4 transition metal,
_{X 3 and _ _} It is C _1-20 alkylsilyl, C _1-20 straight or branched chain alkoxy, or C _1-20 sulfonate group.
According to clause 8,
The first metallocene compound is represented by any one of the following formulas 1-1 to 1-6,
Method for producing polyethylene:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6,
Q ₁ , Q ₂ , A ₁ , M ₁ , X ₁ , X ₂ , and R ₁ to R ₈ are as defined in clause 8,
R' and R" are the same as or different from each other, and each independently represents a C _1-10 hydrocarbyl group.
According to clause 8,
The second metallocene compound is represented by the following formula 2-1 or 2-2,
Method for producing polyethylene:
[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2,
M ₂ , X ₃ , X ₄ , R ₁₀ , and R ₁₆ are as defined in clause 8,
Ar are the same or different from each other and are each independently C _6-20 arylene,
L ₁ and L ₂ are the same as or different from each other, and are each independently C _1-4 alkylene.
According to clause 8,
R ₁₀ and R ₁₆ are each C _1-20 alkylsilyl, or C _1-20 silylalkyl,
Method for producing polyethylene.
According to clause 8,
The polymerization step is performed by adding 35 ppm to 200 ppm of hydrogen gas based on the ethylene content,
Method for producing polyethylene.
Chlorinated polyethylene, produced by reacting the polyethylene of any one of claims 1 and 3 to 7 with chlorine.
According to clause 13,
The chlorinated polyethylene has a pattern viscosity of 90 to 100 measured under 121 ^o C conditions,
Chlorinated polyethylene.
A PVC composition comprising the chlorinated polyethylene of claim 13 and the vinyl chloride polymer.