KR101773722B1 - High density ethylene polymer with excellent processability using supported hybrid metallocene catalyst and methods for producing the same - Google Patents

Abstract

The present invention relates to a high density ethylene-based polymer including a copolymer of an ethylene homopolymer or ethylene, and at least one comonomer selected from the group consisting of alpha olefin, cyclic olefin, and linear, branched and cyclic dienes. A high density polyethylene resin according to the present invention has excellent melting fluidity since the high density polyethylene resin has a wide molecular weight distribution, excellent comonomer distribution characteristics, and a long-chain branch structure, and the high density polyethylene resin has excellent mechanical properties since the comonomer distribution is concentrated in a high-molecular compound. The high density ethylene-based polymer of the present invention has excellent molding processability during processing processes such as extrusion, compression, injection, rotational molding, and the like due to its excellent mechanical properties and melting fluidity.

Description

TECHNICAL FIELD [0001] The present invention relates to a high-density high-density ethylene polymer and a method for producing the same,

The present invention relates to a high density ethylene polymer using a hybrid supported metallocene catalyst and a process for producing the same, and more particularly, to a high density polyethylene polymer which satisfies a balance between excellent mechanical properties and excellent molding processability over conventional high density ethylene polymers .

The high-density ethylene polymer of the present invention relates to a high-density polyethylene polymer having a wide molecular weight distribution and a long chain branching, high melt flowability, excellent workability, high molecular weight and excellent mechanical properties.

The mechanical and thermal properties of polyethylene resins are affected by their molecular weight and density, and thus their application areas are different. In general, the lower the density of the polyethylene polymer is, the better the transparency and the impact strength are, but the physical properties such as heat resistance, hardness and flexural modulus are lowered, and the chemical resistance is lowered.

On the other hand, the higher the density of the polyethylene polymer, the better the physical properties such as heat resistance, hardness and flexural modulus, and the chemical resistance is increased, but the transparency and impact strength are lowered. Therefore, it is very difficult to produce an injection product having excellent impact strength and excellent chemical resistance when producing an injection product using an ethylene copolymer, particularly, various kinds of industrial products such as a cartridge and a pail. Particularly, injection products such as various industrial products demanded by the market require high impact resistance, and therefore the need for such a technology is very high.

High-density polyethylene polymers have been used for many purposes through various molding methods. For example, as a typical method, a film molding is an inflation method in which a molten polymer extrudate is inflated by extruding a high-density polyethylene polymer from a mold while blowing air, and a method of obtaining a molded product of a desired shape, There is a blow molding method in which a high density polyethylene polymer is blown into a mold of a mold and thereafter blowing air into a molten resin in a mold cavity to expand and compress the molten resin on the cavity inner wall to form a molten polymer in the cavity . There is also an injection molding method in which molten high-density polyethylene polymer is injected into a mold cavity to fill the cavity.

The high-density polyethylene polymer has various molding methods, but the common point in these methods is that the high-density polyethylene polymer is first heated to a molten state and molded. Therefore, the behavior of the high-density polyethylene polymer upon heating and melting, that is, the melting property, is an extremely important property in the molding of a high-density polyethylene polymer.

Particularly, in molding such as extrusion, compression, injection molding, or rotary molding, the melting properties, particularly the melt fluidity of the high-density polyethylene polymer, are intrinsic physical properties that determine satisfactory molding processability. The molding processability referred to in the present invention is not limited to the processability at the time of extrusion, compression, injection molding or rotational molding.

Generally, the larger the MI, the MFI and the MFR, the better the melt flowability. Practically, however, since the property required for a polymer as a molding material differs for each molding method, the index used as a standard for the molding processability varies depending on each molding method. For example, in the injection molding method, a high-density polyethylene polymer having a narrow molecular weight distribution tends to be used in order to obtain a molded article having impact resistance.

The high-density polyethylene polymer conventionally used for extrusion, compression, injection or rotary molding is generally produced using a titanium-based Ziegler-Natta catalyst or a chromium-based catalyst.

However, the high-density polyethylene polymer produced by using such a catalyst has a broad molecular weight distribution and can improve the melt fluidity. However, since a low molecular weight component is incorporated therein, the mechanical properties such as impact resistance are remarkably lowered and the comonomer There is a drawback that the distribution is concentrated on the low molecular weight material and the chemical resistance is lowered. Therefore, there is a problem in that high speed in injection molding can not be achieved while maintaining good mechanical properties.

To solve these problems, many researches on metallocene catalysts have been made. U.S. Patent No. 6525150 discloses a metallocene catalyst capable of producing a resin having a narrow molecular weight distribution and uniform distribution of comonomer in the case of a copolymer using uniform active sites of metallocene. However, since the molecular weight distribution is narrow, there is a problem that the mechanical strength is excellent but the molding processability is low.

As described above, in the case of a single metallocene catalyst, since the molecular weight distribution is narrow as a homogeneous active site, the molding processability is not good. Therefore, in the high density polyethylene polymer field in which the balance between mechanical properties and formability is important, application and development of a metallocene catalyst system Is not progressing much.

In order to solve such a problem, it has been proposed to widen the molecular weight distribution by using a plurality of reactors or mixing a large number of metallocene catalysts.

However, when such a method of broadening the molecular weight distribution is used, the moldability is improved, but other properties are inevitably lowered, and a high-density polyethylene polymer having excellent physical properties such as mechanical strength obtained by narrowing the molecular weight distribution can not be obtained.

In addition, a method of improving the melt tension by maintaining the intrinsic viscosity of the catalyst has been proposed, but it has been difficult to improve the melt flowability and thus it is difficult to mold at high speed.

In order to solve the problems of the metallocene catalyst, the melt flowability of the polymer is improved by using a catalyst in which a long chain branch (LCB) is introduced as a side chain to the main chain of the polymer. However, the mechanical properties such as impact resistance, There is a significantly lower problem than when a metallocene catalyst is used.

In another method, a method of producing a polyolefin having a bimodal molecular weight distribution using a catalyst having different reactivity to a comonomer is proposed. However, the polyolefin having such a molecular weight distribution prepared in this manner has improved melt flowability, but has a low molecular weight distribution and low kneading ability. Therefore, there is a problem that it is difficult to obtain a product having uniform physical properties after processing and the mechanical strength is lowered.

Many methods have been proposed to improve the mechanical properties and melt fluidity of high density polyethylene polymers prepared using metallocene catalysts, but most of them have been solved only for linear low density polyolefins. In addition, since metallocene exhibits a tendency to decrease activity as the concentration of comonomer decreases, there is a problem in that it is not economical due to low activity in the production of high density polyolefin.

In the production of a high-density polyolefin, even a catalyst having characteristics of excellent activity and processability in the preparation of a low-density polyolefin has low activity and is uneconomical. In particular, a large amount of fine particles are formed in a gas phase process.

In the gas phase reactor, the activity is an important factor. Since the activity is low, a large amount of fine particles are formed. As a result, a large amount of static electricity is generated, which adversely affects the heat transfer to the reactor wall, thereby lowering the polymerization temperature. This is because a problem of causing the production to stop is generated in the prior art.

In order to solve the above problems, a catalyst for producing a high-density polyolefin polymer having excellent mechanical strength and melt flowability and high activity is continuously required, and improvement is required.

The present invention aims at solving all of the above problems.

The present invention provides a high-density ethylene polymer which simultaneously exhibits mechanical properties, chemical resistance and excellent molding processability which are not exhibited by conventional high-density ethylene polymers, and a method for producing the same.

Another object of the present invention is to provide a method for producing a metallocene catalyst, which has a high comonomer content and a low comonomer content in a high molecular weight compound produced in the presence of a hybrid supported metallocene catalyst to be described later, (ESCR) and a high melt tension, and a process for producing the high-density polyethylene polymer.

It is still another object of the present invention to provide a high-density polyethylene polymer having a broad molecular weight distribution and a long-chain branch structure of a single-ended rod and thus having a small load during processing such as extrusion, compression, injection,

In order to accomplish the objects of the present invention as described above and achieve the characteristic effects of the present invention described below, the characteristic structure of the present invention is as follows.

])와 영점전단점도(zero shear viscosity,

₀)의 관계가 하기 식을 만족한다.The present invention is a density of 0.930 to 0.970 g / cm ³ , An MI of 0.1 to 10 g / 10 min at 190 캜, an MFR of 35 to 100, a long chain branch index (LCBI) of 0.15 to 0.40, and an intrinsic viscosity [

]) And zero shear viscosity,

₀ ) satisfies the following expression.

The present invention relates to a hybrid supported catalyst comprising at least one first metallocene compound represented by the following formula (1), at least one second metallocene compound represented by the following formula (2), and at least one promoter compound Based on the total weight of the ethylene-based polymer.

[Chemical Formula 1]

In the above formula (1), M1 is a Group 4 transition metal of the Periodic Table of the Elements. X ₁ and X ₂ are each independently any one of halogen atoms; R ₁ to R ₁₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted group having 6 to 20 carbon atoms An aryl group, a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms and may be connected to each other to form a ring, and the cyclopentadiene bonded to R 1 to R 5 and the indene bonded to R 6 to R 12 have different structures Is an asymmetric structure, and since the cyclopentadiene and the indene are not connected to each other, a bridge structure can be formed.

(2)

In Formula 2, M2 is a periodic table Group 4 element-transition metal, X _3, X ₄ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms , An aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylamido group having 1 to 20 carbon atoms, an arylamido group having 6 to 20 carbon atoms, , M2 is a periodic table Group 4 element-transition metal, X _3, X ₄ are each independently any one of a halogen atom, R ₁₃ to R ₁₈ is a C 1 -C 10 each independently represent a hydrogen atom, a substituted or unsubstituted An alkyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms, which may be connected to each other to form a ring, R ₂₁ to R ₂₆ each independently represent hydrogen Substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C6-C20 aryl group, or substituted or unsubstituted C7-C40 alkylaryl group, which may be linked together to form a ring and, R _19, R ₂₀ are each independently an alkyl group of a substituted or unsubstituted C1 to C20, they are connected can form a ring, in combination with indene and R ₂₁ to R ₂₆ in combination with R13 to R18 The indene may have the same structure or different structure, and the indene bonding with R ₁₃ to R ₁₈ and the indene bonding with R ₂₁ to R ₂₆ are connected to each other with Si, so that a bridge structure can be formed.

The high density ethylene polymer produced in the present invention in the presence of the hybrid supported metallocene catalyst has excellent melt flowability and excellent impact strength, flexural strength, environmental stress cracking property and melt tension.

1 is a graph showing the relationship between intrinsic viscosity and zero shear viscosity according to Examples and Comparative Examples.
2 is a graph showing the relationship between zero shear viscosity and MI according to Examples and Comparative Examples.

The following description of the invention refers to specific embodiments in which the invention may be practiced by way of illustration. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. It should be understood that the various embodiments of the present invention are different, but need not be mutually exclusive. For example, certain features, structures, and characteristics described herein may be implemented in other embodiments without departing from the spirit and scope of the invention in connection with one embodiment.

The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is to be limited only by the appended claims, along with the full scope of equivalents to which such claims are entitled, if properly explained.

Also, although the present invention uses first, second, etc. to describe various components, it goes without saying that these components are not limited by these terms. These terms are used only to distinguish one component from another.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to facilitate a person skilled in the art to which the present invention pertains.

The present invention includes a high density ethylene polymer that is polymerized in the presence of a hybrid supported metallocene catalyst.

Wherein the polymer is a concept that includes a copolymer.

The hybrid supported metallocene catalysts of the present invention each independently include at least one of the first and second metallocene compounds and at least one cocatalyst compound.

The first metallocene compound, which is a transition metal compound according to the present invention, can be represented by the following formula (1).

The first metallocene compound plays a role of exhibiting high activity in the hybrid supported catalyst and plays a role in improving the melt flowability of the produced polymer.

The first metallocene compound has a low comonomer incorporation property and low molecular weight, and thus improves the processability in processing the polymer.

In addition, high density is formed due to low incorporation of comonomer, and high activity is exhibited even in high density production.

Since the first metallocene compound has an asymmetric structure and a non-bridge structure having different ligands, the comonomer forms a steric hindrance that is difficult to approach the catalytic active site, thereby lowering the incorporation of the comonomer, And exhibit processability and high catalytic activity in the production of rosins.

In the above formula (1), M1 is a Group 4 transition metal of the Periodic Table of the Elements. X ₁ and X ₂ are each independently any one of halogen atoms, and R ₁ to R ₁₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted group having 6 to 20 carbon atoms An aryl group or a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms which may be connected to each other to form a ring, a cyclopentadiene which is bonded to R ₁ to R _5, and an aryl group bonded to R ₆ to R ₁₂ Is an asymmetric structure having different structures, and since the cyclopentadiene and the indene are not connected to each other, a bridge structure can be formed.

In the present invention, the cyclopentadiene bonded to R ₁ to R ₅ of the above-mentioned formula (1), indene bonded to R ₆ to R ₁₂ , indene bonded to R ₁₃ to R ₁₈ of the following formula (2), and R ₂₁ to R ₂₆ An ion or molecule that coordinates with the transition metals (M1 and M2 in formulas (1) and (2)), such as bound indene, is called a ligand.

In the present invention, the term "substituted" as used herein means an aryl group substituted with a substituent such as a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, .

The above-mentioned "hydrocarbon group" means a linear, branched or cyclic saturated or unsaturated hydrocarbon group unless otherwise specified, and the alkyl group, alkenyl group, alkynyl group and the like may be linear, branched or cyclic.

In the specific examples, examples of the transition metal compound represented by the formula (1) include transition metal compounds having the following structures, and mixtures thereof, but are not limited thereto.

In the transition metal compound, M is a Group 4 transition metal such as hafnium (Hf), zirconium (Zr), or titanium (Ti) in the periodic table of the elements, and Me is a methyl group.

The second metallocene compound which is a transition metal compound according to the present invention can be represented by the following general formula (2).

The second metallocene compound plays a role of exhibiting high comonomer incorporation in the hybrid supported catalyst and improves the mechanical properties of the produced polymer.

The second metallocene compound has a high content of comonomer and forms a high molecular weight and has a characteristic of concentrating the distribution of the comonomer in the high molecular weight material, so that the impact strength, the bending strength, the environmental stress cracking property and the melt tension . In addition, the second metallocene compound forms a long-chain branch structure to improve the melt fluidity of a high-molecular-weight high-density polyethylene resin.

The second metallocene compound has a symmetrical structure having various ligands or an asymmetric structure and a bridge structure, so that the comonomer forms a steric hindrance to approach the catalytic active site, thereby increasing the incorporation of the comonomer .

In Formula 2, M2 is the periodic table is a Group 4 transition metal elements, X3, X4 are each independently any one of a halogen atom, R ₁₃ to R ₁₈ each independently represent a hydrogen atom, a substituted or unsubstituted C1 to A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms, which may be connected to each other to form a ring, and R ₂₁ to R ₂₆ each represent A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 7 to 40 carbon atoms, can form, and, R _19, R ₂₀ is the combining and each independently is a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, connected to each other can form a ring, R ₁₃ to R ₁₈ And R ₂₁ to R indene in combination with ₂₆ or structure as each other can be a different structure, the R ₁₃ to indene in combination with indene and R ₂₁ to R ₂₆ in combination with R ₁₈ is because it is mutually connected to the Si bridge structure Can be formed.

In the present invention, the term "substituted" as used herein means an aryl group substituted with a substituent such as a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, . The above-mentioned "hydrocarbon group" means a linear, branched or cyclic saturated or unsaturated hydrocarbon group unless otherwise specified, and the alkyl group, alkenyl group, alkynyl group and the like may be linear, branched or cyclic.

In the specific examples, examples of the transition metal compound represented by Formula 2 include transition metal compounds having the following structures, and mixtures thereof, but are not limited thereto.

In the transition metal compound, M is a Group 4 transition metal such as hafnium (Hf), zirconium (Zr), and titanium (Ti) in the periodic table of the elements. Me is a methyl group and Ph is a phenyl group.

The catalyst composition according to the present invention may contain a cocatalyst compound comprising at least one compound selected from the group consisting of the transition metal compound and the compounds represented by the following formulas (3) to (6).

In Formula 3, AL is aluminum, and R ₂₇ , R < ₂₈ & R ₂₉ is independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group substituted with a halogen having 1 to 20 carbon atoms, and a is an integer of 2 or more, and the above-mentioned formula (3) is a compound having a repeating unit structure.

R _30, R ₃₁ and R ₃₂ each independently represent a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms, Lt; / RTI >

In the formulas (5) and (6), L1 and L2 are neutral or cationic Lewis acids, Z1 and Z2 are Group 13 elements of the Periodic Table of the Elements, A2 and A3 are substituted or unsubstituted C6- Unsubstituted alkyl group having 1 to 20 carbon atoms.

The compound represented by the general formula (3) is aluminoxane, and is not particularly limited as long as it is a common alkylaluminoxane. For example, methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like can be used, and specifically methyl aluminoxane can be used. The alkylaluminoxane may be prepared by adding an appropriate amount of water to trialkylaluminum or by reacting a hydrocarbon compound or an inorganic hydrate salt containing water with trialkylaluminum. Generally, And aluminoxane are mixed together.

As the compound represented by the general formula (4), for example, common alkyl metal compounds can be used. Specifically, there can be mentioned, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tricyclopentyl aluminum, Triethylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron , Tributylboron, tripentafluorophenylboron and the like can be used. More specifically, trimethylaluminum, triisobutylaluminum, tripentafluorophenylboron and the like can be used.

Examples of the compound represented by Chemical Formula 5 or 6 include methyl dioctetylammonium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (phenyl) borate, triethylammonium tetrakis (phenyl) borate, tripropylammonium tetra (Phenyl) borate, tributylammonium tetrakis (phenyl) borate, trimethylammonium tetrakis (p-tolyl) borate, tripropylammonium tetrakis (p- tolyl) borate, trimethylammonium tetrakis ) Borate, triethylammonium tetrakis (o, p-dimethylphenyl) borate, trimethylammonium tetrakis (ptrifluoromethylphenyl) borate, tributylammonium tetrakis (ptrifluoromethylphenyl) borate, tributylammonium Tetrakis (pentafluorophenyl) borate, diethylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphine (Phenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (ptrifluoromethylphenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, trimethylammonium (Phenyl) aluminate, triethylammonium tetrakis (phenyl) aluminate, tripropylammonium tetrakis (phenyl) aluminate, tributylammonium tetrakis (phenyl) aluminate, trimethylammonium tetrakis Alumina, tripropylammonium tetrakis (p-tolyl) aluminate, triethylammonium tetrakis (o, p-dimethylphenyl) aluminate, tributylammonium te (P-trifluoromethylphenyl) aluminate, trimethylammonium tetrakis (ptrifluoromethylphenyl) aluminate, tributylammonium tetrakis (pentafluorophenyl) aluminate, N, N-diethylanilinium tetra (Phenyl) aluminate, N, N-diethylanilinium tetrakis (phenyl) aluminate, N, N-diethylanilinium tetrakis (pentafluorophenyl) aluminate, diethylammonium tetrakis (Phenyl) aluminate, triphenylphosphonium tetrakis (phenyl) aluminate, trimethylphosphonium tetrakis (phenyl) aluminate, triethylammonium tetrakis (phenyl) aluminate, tributylammonium tetrakis But the present invention is not limited thereto. Specifically, it is preferable to use methyl dioctetylammonium tetrakis (pentafluorophenyl) borate ([HNMe (C18H37) 2] + [B (C6F5) 4] -), N, N-dimethylanilinium tetrakis ) Borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, and the like can be used.

In the preparation of the hybrid supported metallocene catalyst according to the present invention, the mass ratio of the transition metal (M1 of Formula 1 and M2 of Formula 2) to the carrier of the first and second metallocene compounds is 1: 1 to 1: 1000 is preferable. Preferably 1: 100 to 1: 500. When the carrier and the metallocene compound are contained at the above mass ratio, they exhibit appropriate supported catalyst activity, which is advantageous in maintaining the activity and economical efficiency of the catalyst.

It is also preferable that the mass ratio of the promoter compound to the carrier represented by the formulas 5 and 6 is 1: 20 to 20: 1, the mass ratio of the promoter compound to the carrier is 1: 100 to 100: 1 desirable.

The mass ratio of the first metallocene compound to the second metallocene compound is preferably 1: 100 to 100: 1. When the cocatalyst and the metallocene compound are contained in the above mass ratio, it is advantageous in maintaining the activity and economical efficiency of the catalyst.

Suitable carriers for preparing the hybrid supported metallocene catalysts according to the present invention can be porous materials having a large surface area.

The first and second metallocene compounds and the co-catalyst compound may be a supported catalyst supported on a support and used as a catalyst. The supported catalyst means a catalyst supported on a carrier in order to maintain good stability and dispersion in order to improve catalytic activity and maintain stability.

The hybrid supported catalyst means that the first and second metallocene compounds are not supported on the carrier, but the catalyst compound is supported on the carrier in a single step. Hybrid support can be said to be much more economical than that carried by each of the shortening of the manufacturing time and the reduction of the solvent use amount.

In this case, the carrier is a solid that disperses and holds a substance having a catalytic function, and is a substance having a large porosity or a large area in order to carry it in a highly dispersed manner so as to increase the exposed surface area of the catalytic functional substance. The carrier should be mechanically, thermally and chemically stable, and examples of the carrier include, but are not limited to, silica, alumina, titanium oxide, zeolite, zinc oxide starch, synthetic polymer and the like.

In addition, the average particle size of the carrier may be from 10 to 250 microns, preferably from 10 to 150 microns, and more preferably from 20 to 100 microns.

The micropore volume of the carrier may be 0.1 to 10 cc / g, preferably 0.5 to 5 cc / g, more preferably 1.0 to 3.0 cc / g.

In addition, the specific surface area of the support may be 1 to 1000 m ² / g, preferably 100 to 800 m ² / g, and more preferably 200 to 600 m ² / g.

Further, when the carrier is silica, the drying temperature of the silica may be 200 to 900 占 폚. Preferably 300 to 800 占 폚, and more preferably 400 to 700 占 폚. When the temperature is less than 200 ° C, the moisture is too much to react with the cocatalyst on the surface, and when the temperature exceeds 900 ° C, the carrier collapses.

The concentration of the hydroxyl group in the dried silica may be 0.1 to 5 mmol / g, preferably 0.7 to 4 mmol / g, and more preferably 1.0 to 2 mmol / g. If it is less than 0.5 mmol / g, the supported amount of the co-catalyst is lowered, and if it exceeds 5 mmol / g, the catalyst component is inactivated.

The hybrid supported metallocene catalyst according to the present invention can be prepared by activating the metallocene catalyst and supporting the activated metallocene catalyst on the carrier. In preparing hybrid supported metallocenes, the cocatalyst can be first supported on the carrier. Activation of the metallocene catalyst can proceed independently and can vary depending on the situation. That is, the first metallocene compound and the second metallocene compound may be mixed and activated and then supported on the carrier. Alternatively, the first and second metallocene compounds may be supported have.

In the preparation of the hybrid supported metallocene catalyst, the solvent of the reaction may be an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as thiochloromethane, a diethyl ether, Most organic solvents such as acetone, ethyl acetate and the like can be used, and toluene and hexane are preferable, but not limited thereto.

The reaction temperature in the production of the catalyst is 0 to 100 ° C, preferably 25 to 70 ° C, but is not limited thereto.

Further, the reaction time in the production of the catalyst is from 3 minutes to 48 hours, preferably from 5 minutes to 24 hours.

Activation of the first and second metallocene compounds can be made by mixing (contacting) the cocatalyst compound. The mixing may be carried out under an inert atmosphere, typically nitrogen or argon, without using a solvent or in the presence of a hydrocarbon solvent.

In addition, the activation temperature of the first and second metallocene compounds may be 0 to 100 캜, preferably 10 to 30 캜.

And, when activating the first and second metallocene compounds with the promoter compound, the stirring time may be 5 minutes to 24 hours, preferably 30 minutes to 3 hours.

The first and second metallocene compounds are dissolved in a hydrocarbon solvent or the like in the form of a liquid catalyst composition. Alternatively, the solvent is removed using a precipitation reaction, followed by vacuum drying at 20 to 200 ° C for 1 to 48 hours But it is not limited thereto.

The process for producing a high density ethylene polymer according to the present invention comprises the step of contacting a hybrid supported metallocene catalyst with at least one olefin monomer to prepare a polyolefin homopolymer or an ethylenic copolymer.

The process for producing the high density ethylene polymer (polymerization reaction) of the present invention can be carried out in a slurry state using an autoclave reactor or a gaseous state using a gas phase polymerization reactor. In addition, the respective polymerization reaction conditions can be variously modified depending on the polymerization method (slurry polymerization, gas phase polymerization) and the desired polymerization result or the form of the polymer. The degree of deformation thereof can be easily performed by a person skilled in the art.

In this case, when the polymerization is carried out in a liquid phase or a slurry, the solvent or the olefin itself can be used as a medium. Examples of the solvent include propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, dichloroethane, And the like. These solvents may be mixed at a certain ratio, but the present invention is not limited thereto.

Examples of the olefin monomer include, but are not limited to, ethylene,? -Olefins, cyclic olefins, dienes, trienes, and styrenes.

The α-olefins include aliphatic olefins having 3 to 12 carbon atoms, for example, 3 to 8 carbon atoms. Specific examples thereof include propylene, 1-butene, 1-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, , 1-hexadecene, 1-heptene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene and 3,4-dimethyl-1-hexene.

The? -Olefins may be homopolymerized or two or more olefins may be alternating, random, or block copolymerized. The copolymerization of the? -Olefins may be carried out by copolymerizing ethylene and an? -Olefin having 3 to 12 carbon atoms, such as 3 to 8 carbon atoms (specifically, ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, 4-methyl-1-pentene, ethylene and 1-octene), and copolymers of propylene and an C4-C8 or C4-C8? -Olefin (specifically, propylene and 1-butene, Methyl-1-pentene, propylene and 4-methyl-1-butene, propylene and 1-hexene, propylene and 1-octene). In the copolymerization of ethylene or propylene with other? -Olefins, the amount of the other? -Olefin may be 99 mol% or less of the total monomer, and preferably 80 mol% or less in the case of the ethylene copolymer.

At this time, preferred examples of the olefin monomer include, but are not limited to, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene and mixtures thereof.

In the method for producing the high-density ethylene polymer of the present invention, the amount of the catalyst composition to be used is not particularly limited. For example, in the polymerization reaction system, the central metal (M, Transition metal) concentration may be from 1 * 10 ^-5 to 9 * 10 ^-5 mol / l.

The concentration of the central metal affects the activity of the catalyst and the properties of the high density ethylene polymer. When the first metallocene compound exceeds the numerical range of the above-mentioned central metal concentration, the activity is increased but the mechanical properties of the resin are lowered. When the first metallocene compound is lower than this numerical value, the activity is decreased and the processability is also decreased. One is not economical due to low physical properties such as one activity, and the generation of static electricity is increased in the gas phase reactor, and stable operation is impossible.

Also, if the concentration of the central metal of the second metallocene compound exceeds the above-described range, the activity is decreased, the mechanical properties are increased but the workability is lowered. If the concentration is less than the above-mentioned range, the activity is increased, There is a problem.

The polymerization temperature and pressure may be varied depending on the reactants, reaction conditions, etc., and therefore the polymerization temperature may be 0 to 200 ° C, preferably 100 to 180 ° C in the case of solution polymerization, and the slurry or In the case of gas phase polymerization, it may be from 0 to 120 캜, preferably from 60 to 100 캜.

Further, the polymerization pressure may be 1 to 150 bar, preferably 30 to 90 bar, and more preferably 10 to 20 bar. The pressure may be by injection of an olefin monomer gas (e. G. Ethylene gas).

For example, the polymerization can be carried out in batch mode (e.g., autoclave reactor), semi-continuous or continuous (e. G., Gas phase polymerisation reactor) and can be carried out in two or more stages with different reaction conditions, The molecular weight of the final polymer can be controlled by varying the polymerization temperature or by injecting hydrogen into the reactor.

The high density ethylene polymer according to the present invention can be obtained by ethylene homopolymerization or copolymerization of ethylene and an alpha olefin using a hybrid supported metallocene compound as a catalyst and has a unimodal distribution of a single rod.

Hereinafter, the high-density ethylene polymer according to the present invention will be specifically described.

The high density ethylene polymer of the present invention may have a density of 0.930 to 0.970 g / cm < ³ >, more preferably 0.950 to 0.965 g / cm < ³ >. If the density of the polymer is 0.930 g / cm ³ or less, it can not exhibit sufficiently high toughness. The density of the polymer 0.970 g / cm ³ By weight, the degree of crystallization becomes too large, and the molded article tends to be brittle and fractured, which is not preferable.

Generally, when the MI (melt index) is increased, the moldability is improved, but the impact resistance is deteriorated. On the other hand, if MI is lowered, the impact resistance and the chemical resistance are improved, but the melt flowability is deteriorated and the moldability is significantly lowered.

For this reason, when MI is increased in order to improve moldability, a method of forming a short-chain branch structure (reduction in density) through copolymerization is generally used to prevent deterioration of impact resistance. However, such a decrease in the density of the ethylene polymer causes deterioration of the toughness of the polymer, and therefore, there is a limit to the method of compensating the impact resistance due to the reduction in density.

The melt flowability referred to in the present invention corresponds mainly to the extrusion load at the time of extruding the molten resin from the extruder, and there is a close relationship (proportional) with the injection moldability (molding processability). MI, MFI, MFR, and the like are used as indexes that serve as standards for such melt fluidity. In the present invention, the MI (melt index) indicates the flowability at 190 DEG C under a load of 2.16 kg, and the MFI indicates the flowability at 190 DEG C under a load of 21.6 kg. MFR represents the ratio of MI to MFI, that is, MFI / MI.

The MI of the high density ethylene polymer of the present invention may be 0.1 to 10 g / 10 min, and preferably 0.5 to 10 g / 10 min. If the MI is less than 0.1 g / 10 min, the molding processability is greatly reduced when used as an injection molding material, and the appearance of the injection product becomes poor. When the MI is much larger than 10 g / 10 min, the impact resistance is greatly lowered.

The high-density polyethylene polymer of the present invention exhibits excellent impact resistance and chemical resistance due to the low MI as described above, unlike the conventional high-density polyethylene polymer, and has a broad molecular weight distribution and a long chain branching, There are those features.

The MFR of the high-density ethylene polymer of the present invention may be 35 to 100, more preferably 37 to 80. [ When the MFR is less than 35, the molding processability is greatly deteriorated when it is used as an injection molding material, and when the MFR exceeds 100, mechanical properties are deteriorated.

FIG. 1 shows a graph of the y-axis zero shear viscosity (Pa.s) according to the intrinsic viscosity (dl / g) of the x-axis. The relationship between the intrinsic viscosity and the zero point shear viscosity As shown in the Mark-Houwink graph, the higher the zero shear viscosity at the same intrinsic viscosity, the greater the long chain branch (LCB) of the polymer is.

It can also be seen from FIG. 1 that the Examples 1 to 7 have a higher zero shear viscosity than the Comparative Examples (1 to 12) at the same intrinsic viscosity values. Thus, according to the present invention, Of the long-chain branch.

Intrinsic viscosity refers to the extreme viscosity without any interaction between solute particles, which means the value obtained by extrapolating the concentration of the solution in the solution obtained by dividing the viscosity by the concentration of the solution to zero, Can be expressed as (viscosity of solution - viscosity of pure solvent) / (viscosity of pure solvent). Since the interaction between solute molecules is negligible in an infinitely dilute solution, the intrinsic viscosity is closely related to the size of the solute molecule alone, that is, the molecular weight.

Long chain branches (LCBs) are known to affect the viscosity and elasticity of molten polymers in general, because they cause physical effects to fill void spaces between polymers. Intrinsic viscosity at the same molecular weight is lowered when the long chain branch in the polymer chain increases and the entanglement of the polymer chain becomes stronger.

The intrinsic viscosity according to an embodiment of the present invention may be 1.1 to 2.0 dL / g, the zero shear viscosity may be 1000 to 100,000 Pa.s, and the intrinsic viscosity (dl / g) and the zero shear viscosity zero shear viscosity, Pa.s) can be expressed by Equation 1 as follows.

[Formula 1]

Further, the relationship between the intrinsic viscosity and the zero point shear viscosity of the above-mentioned formula (1) can be expressed preferably by the following formula (2).

[Formula 2]

FIG. 2 shows a graph of the y-axis zero shear viscosity (Pa.s) according to the melt index (MI) of the x-axis. The relationship between the MI and the zero shear viscosity is shown in FIG. It is relevant that having a high zero shear viscosity (Pa.s) at the same MI means that it has a high molecular weight at the same MI, indicating that it has better mechanical properties at the same MI.

In FIG. 2, it can be seen that Examples 1 to 7 have higher zero shear viscosity at the same MI value than Comparative Examples (1 to 12). Thus, according to the embodiment of the present invention, Is superior to the conventional ethylene polymer in terms of mechanical properties.

The hybrid supported metallocene catalyst according to an embodiment of the present invention can induce the generation of a long chain branch in the high density ethylene polymer produced by incorporating the second metallocene compound as described above, It is possible to prepare a high-density ethylene polymer including a long chain branch (LCB) having a side chain having 6 or more carbon atoms in the chain.

₀)와 고유점도(Intrinsic viscosity, [

])를 이용하여 장쇄분지의 포함을 나타내는 장쇄분지지표 (Long chain branch index, LCBI)를 나타낼 수 있다.In the present invention, as shown in the following formula (3), the zero shear viscosity (Pa.s,

₀ ) and intrinsic viscosity ([

]) Can be used to indicate a long chain branch index (LCBI) indicating the inclusion of the long-chain branch.

[Formula 3]

In Equation 3 of the present invention, k = 298.52 and? = 4.818 were applied based on the data on the linear ethylene polymer.

])가 동일한 값이라면, 영점전단점도(

₀)의 값이 클 때 장쇄분지지표의 값도 커지고, 이는 도 1이 나타내는 것과 동일한 결과를 가지는 것을 알 수 있다.As can be seen from Equation 3, the intrinsic viscosity ([

]) Are the same value, the zero point shear viscosity (

₀ ) is large, the value of the long-chain branch index also becomes large, which is the same as that shown in Fig.

The larger the long-chain branch index, the larger the long chain branch in the polymer, which is an indicator of the relative content of the long chain branch in the polymer. The long chain branch index is affected by the intrinsic viscosity and the zero point shear viscosity as shown in Equation 3 above.

The long chain branch index (LCBI) according to an embodiment of the present invention is 0.15 to 0.40, preferably 0.20 to 0.40.

₀,

₀, n은 유변물성측정장비를 통해 주파수 (

)범위에서의 용융 복합점도(melt complex viscosity,

^*)의 측정값을 곡선 적합(curve fitting) 하여 결정하게 되는 값이다. Further, in the present invention, zero shear viscosity (Pa.s) through a cross model is used by using a complex viscosity measurement value through a rheometer. The complex viscosity, frequency, and zero point shear viscosity can be expressed by a cross model as shown in Equation (4) below.

₀ ,

₀ , n is the frequency (

) ≪ / RTI > range (melt complex viscosity,

^* ) Are determined by curve fitting.

[Formula 4]

^*: 0.1 내지 500 rad/s 범위의 특정 주파수일 때의 복소점도

^* : Complex viscosity at a specific frequency in the range of 0.1 to 500 rad / s

₀: 영점전단점도, lim_?→0

^*(

)=

₀

₀ : zero point shear viscosity, lim _{? → 0}

^* (

) =

₀

: 0.1 내지 500 rad/s범위의 특정 주파수

: A specific frequency in the range of 0.1 to 500 rad / s

₀: 전단담화(Shear thinning)가 시작되는 지점 또는 Newtonian plateau가 끝나는 지점에서의 주파수

₀ : Frequency at which the shear thinning begins or at which the Newtonian plateau ends

n: Power-law flow behavior index (0 < n < 1)

The high-density ethylene polymer of the present invention not only has excellent mechanical strength by having a low MI, but also has a high molecular weight as compared with other ethylene polymers having similar MI as shown in Fig. 2, There are excellent features.

In addition, it shows a high MFR even though it has a low MI because it contains a long-chain branch, which shows that the molding processability is superior to the conventional high density ethylene polymer.

The high density ethylene polymers of the present invention can be used as injection molding, compression molding, and rotational molding materials.

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

The first metallocene  compound Manufacturing example  One. [ Indenyl ( cyclopentadienyl )] ZrCl ₂

(N-BuLi) hexane solution (17 ml, 0.043 mol) was added to the hexane solution after cooling to -30 ° C. Was slowly dropped and stirred at room temperature for 12 hours. The white suspension was filtered through a glass filter to sufficiently dry the white solid to obtain an indium lithium salt (yield: 99% yield).

Inden-lithium salt (1.05 g, 8.53 mmol) slowly to the _{CpZrCl 3 (2.24 g, 8.53 mmol} ) and ether (30 mL) to the slurry dissolved, then it was cooled to -30 ℃. To this ether solution, an indenyl lithium salt dissolved in ether (15 mL) was slowly dropped and stirred for 24 hours to obtain [Indenyl (cyclopentadienyl)] ZrCl ₂ (yield: 97%). Here, Cp means cyclopentadienyl.

The first metallocene  compound Manufacturing example  2. [2-methyl benzeindenyl  ( cyclopentadienyl )] ZrCl ₂

2-methylbenzeindene was used in the same manner as in Preparation Example 1 to give [2-methyl benzenindenyl (cyclopentadienyl)] ZrCl ₂ (yield: 95%).

The first metallocene  compound Manufacturing example  3. [2-Phenyl benzeindenyl  (tetramethylcyclopentadienyl)] ZrCl ₂

2-methylbenzeindene and tetramethylcyclopentadiene were used in the same manner as in Preparation Example 1 to give [2-phenylbenzeneindenyl (tetramethylcyclopentadienyl)] ZrCl ₂ (yield: 93%).

The first metallocene  compound Manufacturing example  4. [ fluorenyl  ( cyclopentadienyl )] ZrCl ₂

(2-phenyl benzindenyl) tetrakis (triphenylphosphine)] ZrCl ₂ (yield: 92%) was obtained in the same manner as in Production Example 1, using fluorene and cyclopentadiene.

The second metallocene  compound Manufacturing example  5. Me ₂ Si {2-methyl-4- (One- naphthyl )} ₂ ZrCl ₂

Manufacturing example  5-1: Preparation of ligand compound

The 2-methyl-4-bromo indene (2 g, 1 eq), Pd (PPh 3) 4 (553 mg, 0.05 eq), 1-NaphB (OH) 2 (2.14 g, 1.3 eq) THF, MeOH solution ( 2-methyl-4- (1-naphthyl) propane was added to the degassed aqueous K ₂ CO ₃ solution (2.0 M, 3.3 eq) at room temperature and refluxed at 80 ° C. for 12 hours. indene. N-BuLi (7.8 mL, 1.1 eq, 1.6 M in Hexane) was added slowly at -30 ° C, the temperature was slowly raised to room temperature, and 12 hours Lt; / RTI &gt; The resulting solid was filtered, washed with hexane and dried under vacuum to give 2-methyl-4- (1-naphthyl) indenyl lithium.

2-methyl-4- (1-naphthyl) indenyl lithium (1.88 g, 2 eq) SiMe ₂ Cl ₂ (462 mg, 1 eq) was slowly added to 13 mL of toluene, THF and 3 mL at -30 ° C, The resulting mixture was gradually stirred and stirred at 55 ° C for 12 hours to obtain 1.97 g (97%) of dimethylbis {2-methyl-4- (1-naphthyl) indenyl)} silane.

Manufacturing example  5-2: 2nd Metallocene  Compound manufacturing

N-BuLi (1.32 mL, 2.2 eq, 1.6 M in Hexane) was added slowly at -30 ° C, and the temperature was gradually lowered to room temperature And stirred for 12 hours to form a dilithium salt. ZrCl ₄ (435 mg, 1 eq) was slowly added to the dilithium salt slurry and stirred for 12 hours. The solvent was removed in vacuo and washed with THF and MC to give Me ₂ Si {2-methyl-4- (1-naphthyl)} ₂ ZrCl ₂ (94% yield).

The second metallocene  compound Manufacturing example  6. Me ₂ Si {2-methyl-4- (2- naphthyl )} ₂ ZrCl ₂

Manufacturing example  6-1: Preparation of ligand compound

2-methyl-7- (2-naphthyl) indene was used to prepare Dimethylbis {2-methyl-4- (2-naphthyl) indenyl)} silane (yield: 51%) .

Manufacturing example  6-2: 2nd Metallocene  Compound manufacturing

The yield of Me ₂ Si {2-methyl-4- (2-naphthyl)} ₂ ZrCl ₂ was obtained in the same manner as in Production Example 5-2 using the compound of Preparation Example 6-1.

The second metallocene  compound Manufacturing example  7. ( Me ₂ Si (2-methyl-4-phenyl indenyl ) ₂ ZrCl ₂ )

Manufacturing example  7-1: Preparation of ligand compound

2-methyl-4-bromo indene (7 g, 1 eq) and Ni (dppp) Cl ₂ (363 mg, 0.02 eq) were added to Ether (100 mL) and PhMgBr 3.0 M in ether (13.3 g, 1.05 eq) is added over 1 hour. The temperature is slowly raised to room temperature (25 캜) and refluxed at 50 캜 for 12 hours. After completion of the reaction, the solution is immersed in an ice bath, and the pH is lowered to 4 by addition of 1N HCl acid. The organic layer is extracted with a separatory funnel, and then the water is removed by treatment with MgSO ₄ . Filtration and drying of the solvent affords 2-methyl-4- (phenyl) indene (yield: 97%). Me ₂ Si (2-methyl-4-phenyl indenyl) _{2 was} prepared in the same manner as in Production Example 5-1 using 2-methyl-4- (phenyl) indene. Here, dppp means 1,3-bis (diphenylphosphino) propane.

Manufacturing example  7-2: 2nd Metallocene  Compound manufacturing

It was prepared in _{Me 2 Si (2-methyl-} 4-phenylindene) in the same manner as in Production Example 5-2 by using a _{2 Me 2 Si (2-methyl} -4-phenyl indenyl) 2 ZrCl 2 ( yield: 90% ).

Mixed bearing Metallocene  catalyst Manufacturing example  8

Since the first and second metallocene compounds and the co-catalyst methylaluminoxane (MAO) react with moisture or oxygen in the air, the activity is lost. Therefore, all the experiments are carried out under a nitrogen condition using a glove box and a Schlenk technique Respectively. The 10L supported catalytic reactor was washed and removed foreign matters. After the reactor was closed at 110 ° C for 3 hours or more, the reactor was completely vacuumed to remove water and the like.

A 10 wt% methylaluminum oxalate (MAO) solution (methylaluminoxane: 1188 g) was added to 2.862 g of the compound of Preparation Example 1 and 9 g of the compound 3.46 of Preparation Example 7-2, and the mixture was stirred at room temperature for 1 hour. After 300 g of silica (XPO2402) was charged to the reactor, 900 mL of purified toluene was added to the reactor and stirred. After the stirring step for 1 hour was completed, a mixed solution of the first metallocene compound, the second metallocene compound and methyl aluminum oxalate was added while stirring the reactor. The reactor was heated to 60 DEG C and stirred for 2 hours.

After the precipitation reaction, the supernatant was removed, washed with 1 L of toluene, and vacuum dried at 60 ° C for 12 hours.

Mixed bearing Metallocene  catalyst Manufacturing example  9

The procedure of Production Example 8 was repeated except that 2.389 g of the compound of Preparation Example 2 and 4.387 g of the compound of Preparation Example 7-2 were used.

Mixed bearing Metallocene  catalyst Manufacturing example  10

2.712 g of the compound of Preparation Example 3, and 3.046 g of the compound of Preparation Example 6-2.

Mixed bearing Metallocene  catalyst Manufacturing example  11

The procedure of Production Example 8 was repeated except that 2.662 g of the compound of Preparation Example 4 and 3.712 g of the compound of Preparation Example 5-2 were used.

Example  One

The mixed supported metallocene catalyst obtained in Preparation Example 8 was fed into a continuous polymerization reactor of a fluidized bed gas process to prepare an olefin polymer. 1-hexene was used as the comonomer, the ethylene pressure in the reactor was 15 bar, the hydrogen / ethylene molar ratio was 0.084%, and the polymerization temperature was maintained at 80 to 90 ° C.

Example  2

The mixed supported metallocene catalyst obtained in Preparation Example 9 was fed into a continuous polymerization reactor of a fluidized bed gas process to prepare an olefin polymer. 1-hexene was used as the comonomer, the reactor ethylene pressure was 14.4 bar, the hydrogen / ethylene molar ratio was 0.101%, and the polymerization temperature was maintained at 80 to 90 ° C.

Example  3

The olefin polymer was prepared by feeding the hybrid supported metallocene catalyst obtained in Preparation Example 10 into a continuous polymerizer of a fluidized bed gas process. 1-hexene was used as the comonomer, the reactor ethylene pressure was 14.7 bar, the hydrogen / ethylene molar ratio was 0.123%, and the polymerization temperature was maintained at 80 to 90 ° C.

Example  4

The mixed supported metallocene catalyst obtained in Preparation Example 11 was fed into a continuous polymerizer of a fluidized bed gas process to prepare an olefin polymer. 1-hexene was used as the comonomer, the reactor ethylene pressure was 15 bar, the hydrogen / ethylene molar ratio was 0.125%, and the polymerization temperature was maintained at 80-90 ° C.

Example  5

The mixed supported metallocene catalyst obtained in Preparation Example 9 was fed into a continuous polymerization reactor of a fluidized bed gas process to prepare an olefin polymer. 1-hexene was used as the comonomer, the ethylene pressure in the reactor was 15.2 bar, the hydrogen / ethylene molar ratio was 0.137%, and the polymerization temperature was maintained at 80-90 ° C.

Example  6

The olefin polymer was prepared by feeding the hybrid supported metallocene catalyst obtained in Preparation Example 10 into a continuous polymerizer of a fluidized bed gas process. 1-hexene was used as the comonomer, the ethylene pressure in the reactor was 14.9 bar, the hydrogen / ethylene molar ratio was 0.136%, and the polymerization temperature was maintained at 80-90 ° C.

Example  7

The mixed supported metallocene catalyst obtained in Preparation Example 11 was fed into a continuous polymerizer of a fluidized bed gas process to prepare an olefin polymer. 1-hexene was used as the comonomer, the reactor ethylene pressure was 14.8 bar, the hydrogen / ethylene molar ratio was 0.152%, and the polymerization temperature was maintained at 80 to 90 ° C.

Comparative Example  One

Commercial product HDPE 7303 (SK General Chemicals) was used.

Comparative Example 1 has a density of 0.9523 g / cm ³ according to ASTM D 1505 and a melt index (MI) according to ASTM D 1238 of 2.1 g / 10 min.

Comparative Example  2

Commercial product HDPE ME2500 (LG Chem) was used.

Comparative Example 2 has a density of 0.9538 g / cm ³ according to ASTM D1505 and a melt index (MI) according to ASTM D1238 of 2.1 g / 10min.

Comparative Example  3

Commercial product HDPE C910A (Hanwha total) was used.

Comparative Example 3 had a density of 0.9556 g / cm ³ according to ASTM D1505 and a melt index (MI) of 2.4 g / 10 min according to ASTM D1238.

Comparative Example  4

Commercial product HDPE 7390 (Hanwha Chemical) was used.

Comparative Example 4 had a density of 0.9532 g / cm ³ according to ASTM D1505 and a melt index (MI) of 4.2 g / 10min according to ASTM D1238.

Comparative Example  5

A commercial product, HDPE M850 (Korea Emulsified), was used.

Comparative Example 5 had a density of 0.9642 g / cm ³ according to ASTM D 1505 and a melt index (MI) according to ASTM D 1238 of 4.9 g / 10 min.

Comparative Example  6

Commercial product HDPE 2200J (Lotte Chemical) was used.

Comparative Example 6 has a density of 0.9582 g / cm ³ according to ASTM D 1505 and a melt index (MI) according to ASTM D 1238 of 5.1 g / 10 min.

Comparative Example  7

Commercial product ME6000 (LG Chem) was used.

Comparative Example 7 had a density of 0.9621 g / cm ³ according to ASTM D 1505 and a melt index (MI) according to ASTM D 1238 of 5.8 g / 10 min.

Comparative Example  8

Commercial product HDPE 7210 (SK General Chemicals) was used.

Comparative Example 8 has a density of 0.9579 g / cm ³ according to ASTM D1505 and a melt index (MI) of 6.1 g / 10 min according to ASTM D1238.

Comparative Example  9

A commercial product, HDPE M680 (Korea Emulsified), was used.

Comparative Example 9 has a density of 0.9562 g / cm ³ according to ASTM D 1505 and a melt index (MI) according to ASTM D 1238 of 6.9 g / 10 min.

Comparative Example  10

Commercial product HDPE 7600 (Hanwha Chemical) was used.

Comparative Example 10 had a density of 0.9592 g / cm ³ according to ASTM D 1505 and a melt index (MI) according to ASTM D 1238 of 7.2 g / 10 min.

Comparative Example  11

Commercial product HDPE 2210J (Lotte Chemical) was used.

Comparative Example 11 had a density of 0.9580 g / cm ³ according to ASTM D 1505 and a melt index (MI) according to ASTM D 1238 of 8.0 g / 10 min.

Comparative Example  12

Commercial product ME8000 (LG Chem) was used.

Comparative Example 12 had a density of 0.9592 g / cm ³ according to ASTM D1505 and a melt index (MI) of 8.0 g / 10min according to ASTM D1238.

&Lt; Method for measuring physical properties &

1) Density was measured according to ASTM D1505.

2) MI, MFI and MFR

The melt flow MI was an extrusion rate of 10 minutes at a load of 2.16 kg and was measured according to ASTM 1238 at a measurement temperature of 190 占 폚.

The MFI was an extrusion amount of 10 minutes at a load of 21.6 kg and measured according to ASTM 1238 at a measurement temperature of 190 占 폚.

MFR represents the ratio of MI to MFI, that is, MFI / MI.

₀)은 TA사의 ARES 유변물성측정장비로 측정된 주파수(frequency)에 대한 복소점도(complex viscosity)의 값을 크로스 모델(Cross model)을 통하여 곡선 적합(curve fitting) 된 값을 사용한다. 3) Zero shear viscosity,

₀ ) uses the value of the complex viscosity for the frequency measured by TA's ARES Rheometer to measure the curve fitting through the cross model.

])는 ISO1628-3에 따라 측정되었다.4) Intrinsic viscosity [

]) Was measured according to ISO1628-3.

 Table 1 shows the polymerization conditions of Examples 1 to 7.

Ethylene pressure
(bar) Hydrogen / Ethylene mole ratio (%) 1-hexene / ethylene molar ratio (%) Catalytic activity
(gPE / gCat) Example 1 15.0 0.084 0.128 4800 Example 2 14.4 0.101 0.161 4900 Example 3 14.7 0.123 0.131 4800 Example 4 15.0 0.125 0.157 5100 Example 5 15.2 0.137 0.154 5000 Example 6 14.9 0.136 0.147 5100 Example 7 14.8 0.152 0.152 5200

Table 2 shows the above-mentioned measurement data of the physical properties.

density
(g / cm ³⁾ MI
(g / 10 min) MFR LCBI
(Long-run branch indicator) Example 1 0.9542 1.1 56.1 0.309 Example 2 0.9582 1.6 46.9 0.248 Example 3 0.9572 2.5 43.6 0.325 Example 4 0.9563 2.6 42.7 0.315 Example 5 0.9562 6.3 40.5 0.278 Example 6 0.9534 6.9 39.7 0.374 Example 7 0.9560 8.5 37.0 0.315 Comparative Example 1 0.9523 2.1 37.4 0.029 Comparative Example 2 0.9538 2.1 28.5 0.073 Comparative Example 3 0.9556 2.4 28.5 0.064 Comparative Example 4 0.9532 4.2 26.1 0.075 Comparative Example 5 0.9642 4.9 34.9 0.111 Comparative Example 6 0.9582 5.1 32.6 0.042 Comparative Example 7 0.9621 5.8 30.1 0.078 Comparative Example 8 0.9579 6.1 35.4 0.111 Comparative Example 9 0.9562 6.9 30.4 0.051 Comparative Example 10 0.9592 7.2 27.8 0.143 Comparative Example 11 0.9580 8.0 27.6 0.001 Comparative Example 12 0.9592 8.0 28.5 0.054

 The second metallocene compound represented by the general formula (2) has a bridge structure form, which protects the catalytic active site and facilitates comonomer accessibility to the catalytic active site, thereby having properties of excellent comonomer penetration. And has a characteristic that the catalytic active sites are stabilized and high molecular weight is formed as compared with the unbridged structure in which the ligands are not connected to each other.

However, when the second metallocene compound represented by the general formula (2) is used singly, the activity is too low to be economical and too much high-molecular weight compounds are formed, which deteriorates processability.

As shown in Table 2, the high-density polyethylene resin prepared using the hybrid supported metallocene catalyst according to the embodiment of the present invention has higher long-chain branch index (relative to the conventional polyethylene resin having comparable MI value (Comparative Examples 1 to 12) (LCBI). It shows a relatively high MFR in spite of low MI due to the inclusion of a long chain branch, and thus it can be confirmed that it has excellent molding processability (injection processability).

As described above, the high-density ethylene polymer of the present invention can be confirmed to contain a long-chain branch from the relationship between the intrinsic viscosity and the zero shear viscosity, It can be seen that the high density ethylene polymer according to the embodiment of the present invention has excellent processability.

From FIG. 2, it can be seen that the high-density ethylene polymer of the present invention has a low MI and a high molecular weight as compared with the conventional ethylene polymer having a similar MI. It can be seen that the high-density ethylene polymer according to the embodiment has excellent mechanical properties.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood by those skilled in the art that various changes may be made and equivalents may be resorted to without departing from the scope of the appended claims.

Claims (20)

At least one monomer selected from the group consisting of alpha-olefin monomers and ethylene;
Wherein the polymer comprises a long chain branch (LCB) and the long chain branching index (LCBI) is from 0.15 to 0.40;
A density of 0.930 to 0.970 g / cm &lt; ^{3 &} gt ;;
MI is from 0.5 to 10 g / 10 min;
An MFR of 35 to 100;
Intrinsic viscosity [

]) And zero shear viscosity,

₀ ) is expressed by the following expression 1,
[Formula 1]

The polymer comprises at least one first metallocene compound represented by the following formula (1), at least one second metallocene compound represented by the following formula (2), at least one promoter compound and a carrier Characterized in that the catalyst is polymerized using a hybrid supported metallocene catalyst,
[Chemical Formula 1]

In Formula 1,
M1 is a Group 4 transition metal of the Periodic Table of the Elements;
X ₁ and X ₂ are each independently any one of halogen atoms;
R ₁ to R ₁₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms And may be connected to each other to form a ring;
The cyclopentadiene combined with R ₁ to R ₅ and the indene bonded with R ₆ to R ₁₂ have an asymmetric structure having a different structure;
The cyclopentadiene and the indene are not connected to each other to form a bridge structure;
(2)

In Formula 2,
M2 is a Group 4 transition metal of the Periodic Table of Elements;
X ₃ and X ₄ are each independently any one of halogen atoms;
R ₁₃ to R ₁₈ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms And may be connected to each other to form a ring;
R ₂₁ to R ₂₆ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms And may be connected to each other to form a ring;
R ₁₉ and R ₂₀ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and may be connected to each other to form a ring;
The indene bonded to R ₁₃ to R ₁₈ and the indene bonded to R ₂₁ to R ₂₆ may be the same or different from each other;
The indene bonding with R ₁₃ to R ₁₈ and the indene bonding with R ₂₁ to R ₂₆ are connected with each other to form a bridge structure,
Wherein the first metallocene compound comprises at least one compound selected from the group consisting of compounds having the following structures.

delete delete The method according to claim 1,
The above-mentioned alpha-olefin-
Pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1 -Hexadecene and 1-aidocene, and at least one selected from the group consisting of hexadecene and 1-isocene. The method according to claim 1,
Wherein when the high density ethylene polymer is a copolymer of ethylene and the alpha olefin monomer, the content of the alpha olefin monomer is 0.1 to 10% by weight. The method according to claim 1,
Wherein the high-density ethylene-based polymer is an injection, compression, or rotational molding material. delete delete The method according to claim 1,
Wherein the second metallocene compound comprises at least one compound selected from the group consisting of compounds having the following structures.

The method according to claim 1,
Wherein the co-catalyst compound comprises at least one of compounds represented by the following Chemical Formulas (3) to (6).
(3)

In Formula 3,
AL is aluminum;
R ₂₇ , R ₂₈ and R ₂₉ are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms;
a is an integer of 2 or more,
[Chemical Formula 4]

In Formula 4,
A1 is aluminum or boron;
R ₃₀ , R ₃₁ and R ₃₂ are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with a halogen having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms,
[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas (5) and (6)
L1 and L2 are each independently a neutral or cationic Lewis acid;
Z1 and Z2 are each independently a Group 13 element of the Periodic Table of Elements;
A 2 and A 3 are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. 11. The method of claim 10,
The cocatalyst compound represented by the general formula (3)
And at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane. 11. The method of claim 10,
The promoter compound represented by the general formula (4)
There may be mentioned aluminum, triethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum , Dimethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributyl And at least one compound selected from the group consisting of boron and tripentafluorophenylboron. 11. The method of claim 10,
The promoter compound represented by the above formula (5) or (6)
(Phenyl) borate, triethylammonium tetrakis (phenyl) borate, tripropylammonium tetrakis (phenyl) borate, tributylammonium &lt; RTI ID = 0.0 & (P-tolyl) borate, trimethylammonium tetrakis (o, p-dimethylphenyl) borate, triethylammonium tetrakis (triphenylphosphine) borate, triethylammonium tetrakis (p-dimethylphenyl) borate, trimethylammonium tetrakis (ptrifluoromethylphenyl) borate, tributylammonium tetrakis (ptrifluoromethylphenyl) borate, tributylammonium tetrakis , Diethylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (phenyl) borate, N, N-diethylanilinium tetrakis (phenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium (Pentafluorophenyl) borate, trimethylammonium tetrakis (phenyl) aluminate, trimethylammonium tetrakis (triphenylphosphine) borate, triphenylcarbeniumtetrakis (ptrifluoromethylphenyl) borate, triphenylcarbeniumtetrakis (Phenyl) aluminate, triethylammonium tetrakis (phenyl) aluminate, tripropylammonium tetrakis (phenyl) aluminate, tributylammonium tetrakis (p-tolyl) aluminate, triethylammonium tetrakis (o, p-dimethylphenyl) aluminate, tributylammonium tetrakis (ptrifluoromethylphenyl) N, N-diethylanilinium tetrakis (phenyl) aluminate, N, N-diethylanilinium tetrakis (triphenylphosphine) aluminate, tributylammonium tetrakis (pentafluorophenyl) N, N-diethylanilinium tetrakis (pentafluorophenyl) aluminate, diethylammonium tetrakis (pentafluorophenyl) aluminate, triphenylphosphine At least one selected from the group consisting of boron tetrakis (phenyl) aluminate, trimethylphosphonium tetrakis (phenyl) aluminate, triethylammonium tetrakis (phenyl) aluminate, and tributylammonium tetrakis Based polymer. The method according to claim 1,
The total mass of the transition metal of the first metallocene compound and the second metallocene compound and the mass ratio of the carrier is 1: 1 to 1: 1000,
Wherein the mass ratio of the first metallocene compound to the second metallocene compound is from 1: 100 to 100: 1. 11. The method of claim 10,
The mass ratio of the co-catalyst compound represented by the above formulas 3 and 4 to the carrier is 1: 100 to 100: 1,
Wherein the mass ratio of the co-catalyst compound represented by the general formulas (5) and (6) to the carrier is 1: 20 to 20: 1. The method according to claim 1,
Wherein the carrier comprises:
At least one selected from the group consisting of silica, alumina, titanium oxide, zeolite, zinc oxide, and starch;
An average particle size of 10 to 250 microns;
The micropore volume is 0.1 to 10 cc / g;
And a specific surface area of 1 to 1000 m ² / g. (a) preparing at least one first metallocene compound represented by the following formula (1), at least one second metallocene compound represented by the following formula (2), and at least one promoter compound ;
(b) stirring the prepared first metallocene compound, the second metallocene compound and the co-catalyst compound at 0 to 100 ° C for 5 minutes to 24 hours to prepare a catalyst mixture;
(c) adding the catalyst mixture to a reactor in which a carrier and a solvent are present, and stirring the mixture at 0 to 100 ° C for 3 minutes to 48 hours to prepare a hybrid supported catalyst composition; And
(d) adding at least one alpha olefin monomer selected from the group consisting of the above-mentioned hybrid supported catalyst composition and alpha olefin and ethylene into an autoclave reactor or a gas phase polymerization reactor at a temperature of 60 to 100 DEG C and a pressure of 10 to 20 bar &lt; / RTI &gt; wherein the step of polymerizing comprises the step of polymerizing the high-density ethylene polymer according to claim 1 in the environment of a high density ethylene polymer.
[Chemical Formula 1]

In Formula 1,
M1 is a Group 4 transition metal of the Periodic Table of the Elements;
X ₁ and X ₂ are each independently any one of halogen atoms;
R ₁ to R ₁₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms And may be connected to each other to form a ring;
The cyclopentadiene combined with R ₁ to R ₅ and the indene bonded with R ₆ to R ₁₂ have an asymmetric structure having a different structure;
The cyclopentadiene and the indene are not connected to each other to form a bridge structure;
(2)

In Formula 2,
M2 is a Group 4 transition metal of the Periodic Table of Elements;
X ₃ and X ₄ are each independently any one of halogen atoms;
R ₁₃ to R ₁₈ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms And may be connected to each other to form a ring;
R ₂₁ to R ₂₆ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms And may be connected to each other to form a ring;
R ₁₉ and R ₂₀ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and may be connected to each other to form a ring;
The indene bonded to R ₁₃ to R ₁₈ and the indene bonded to R ₂₁ to R ₂₆ may be the same or different from each other;
The indene bonds with R ₁₃ to R ₁₈ and the indene with R ₂₁ to R ₂₆ are connected to each other to form a bridge structure. 18. The method of claim 17,
Wherein the co-catalyst compound comprises at least one of compounds represented by the following formulas (3) to (6).
(3)

In Formula 3,
AL is aluminum;
R ₂₇ , R ₂₈ and R ₂₉ are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms;
a is an integer of 2 or more,
[Chemical Formula 4]

In Formula 4,
A1 is aluminum or boron;
R ₃₀ , R ₃₁ and R ₃₂ are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with a halogen having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms,
[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas (5) and (6)
L1 and L2 are each independently a neutral or cationic Lewis acid;
Z1 and Z2 are each independently a Group 13 element of the Periodic Table of Elements;
A 2 and A 3 are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. 18. The method of claim 17,
The step (c)
Separating the supernatant by a precipitation reaction of the hybrid supported catalyst composition;
Removing the separated supernatant and washing the remaining catalyst composition precipitate with a solvent;
Vacuum drying the washed catalyst composition at 20 to 200 DEG C for 1 to 48 hours. 18. The method of claim 17,
The alpha olefin monomer may be selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, -Tetradecene, 1-hexadecene, and 1-aidocene. 2. The method according to claim 1,

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