WO2019156482A1 - Method for preparing supported hybrid metallocene catalyst - Google Patents

Abstract

The present invention relates to a method for preparing a supported hybrid metallocene catalyst and, more particularly, to a method in which a first metallocene compound is supported, a promoter is supported by means of split addition, in which a part of the promoter is primarily added at 100°C to 150°C and the rest is secondarily added at -5°C to 40°C, and a second metallocene compound is supported. Therefore, the present invention enables enhancement of the promotor supporting rate in a supported catalyst, maintenance of high catalyst activity, increased morphology (reduction of fine particle generation) and apparent density of a generated polymer, and increased settling efficiency and also can efficiently be used for preparation of polyolefin showing increased molecular weight distribution and thus having enhanced processability.

Description

 [Name of invention]

 Manufacturing Method of Hybrid Supported Metallocene Catalyst [Technical Field]

 Citation with Related Applications

 This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0015903 dated February 8, 2018 and Korean Patent Application No. 10-2019-0013833 dated February 1, 2019. All content disclosed in the literature is included as part of this specification. The present invention relates to a method for producing a hybrid supported metallocene catalyst and a method for producing a polyolefin using the catalyst prepared accordingly.

Background Art

Generally, the polymerization process of olefin is classified into high pressure process, solution process, slurry process, and gas phase process, and various efforts are made to prepare an olefin polymer having desired properties by applying various metallocene catalysts to the polymerization process. have. Metallocene catalysts used in the production of polyethylene using slurries and gas-phase polymerization processes must be firmly immobilized on a suitable carrier to avoid reactor fouling due to leaching. In particular, since the apparent density of the polymer is closely related to the reactor unit productivity, not only should the catalyst activity be high, but also the apparent density of the polymer should be high. In order to manufacture a supported metallocene catalyst, a technique is generally used to increase the amount of aluminoxane, which is a co-catalyst, while simultaneously using a high active metallocene catalyst to increase catalyst activity. However, in the case of the highly active supported catalyst, polymerization occurs first on the surface of the carrier, and the resulting polymer crystallizes to inhibit the diffusion of the next monomer (momomer di ffusion). 2019/156482 1 »（： 1 ^ 1 {2019/001535

It is common for apparent density to become low by forming a hollow polymer. In order to solve this problem, there is an attempt to control the rate of diffusion to the inside of the carrier of a polymerized monomer such as ethylene by prepolymerization ( _{1 1 01} , ₆₁ ^ ₂ ^ 1 ₀₁₁₎ at low temperature and low pressure, but additionally, a polymerization reactor is installed. There is a problem that must be done. In addition, there is a supporting method for improving the supporting efficiency by treating the hydroxy group on the surface of the carrier with aluminum chloride, etc., but the catalyst manufacturing cost increases and can reduce the catalyst uniformity due to side reactions. Meanwhile, the metallocene catalyst is composed of a combination of a main component a metallocene compound as a main catalyst mainly composed of an aluminum organometallic compound of the cocatalyst, the single site catalyst as a sort of homogeneous catalyst complexes such as metal (not _1¾16 ..) The molecular weight distribution is narrow according to the characteristics of the single active site, and the homogeneous composition of the comonomer is obtained, and the stereoregularity, copolymerization characteristic, molecular weight, It has the property to change the crystallinity. However, when the metallocene catalyst is to be supported on a solid carrier to increase the bulk density of a polymer such as polyolefin, in many cases, there is a problem in that the activity of the catalyst and the molecular weight distribution of the polymer are lowered. Accordingly, there is a continuing need for a method for preparing a hybrid supported metallocene catalyst capable of producing a polyolefin polymer having both an apparent density and a molecular weight distribution of the polymer while maintaining high active catalyst properties to solve the above disadvantages.

Detailed Description of the Invention

 [Technical problem]

The present invention is to provide a method for preparing a hybrid supported metallocene catalyst capable of producing a polyolefin polymer having both an apparent density and a molecular weight distribution of the polymer while maintaining high active catalyst properties. 2019/156482 1 »（： 1 ^ 1 {2019/001535

In addition, the present invention is to provide a method for producing a polyolefin using a catalyst prepared by the method as described above. Technical Solution

 According to one embodiment of the invention, the step of supporting at least one first metallocene compound on the silica carrier;

 Contacting the silica carrier on which the first metallocene compound is supported with at least one aluminum-based promoter compound to support the aluminum-based promoter compound on the silica carrier; and

 Supporting at least one second metallocene compound on the silica carrier on which the aluminum-based promoter compound is supported;

 Including,

The aluminum-based promoter compound is 60% by weight to 90 of the total amount

Provided is a method for producing a hybrid supported metallocene catalyst supported on a carrier. On the other hand, according to another embodiment of the invention, there is provided a method for producing a polyolefin comprising the step of polymerizing the olefin monomer in the presence of a hybrid supported metallocene catalyst prepared according to the method as described above. In the present invention, the terms first, second, etc. are used to describe various components, which terms are only used to distinguish one component from another component. In addition, the terminology used herein is for the purpose of describing example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the words "include", "include" or "have" 2019/156482 1 »（： 1 ^ 1 {2019/001535

The term is intended to designate that the implemented feature, number, step, component, or combination thereof exists, and preliminary to the presence or addition of one or more other features, numbers, steps, components, or a combination thereof. It should be understood to not exclude it.

₅

As the invention allows for various changes and numerous modifications, particular embodiments will be illustrated and described in detail below. However, it should be understood to include not intended to limit the invention to the particular form disclosed, and ₁₀ all included in the spirit and scope of the present invention changes, equivalents and substitutes. Hereinafter, a method of preparing a hybrid supported metallocene catalyst and a method of preparing polyolefin using the catalyst prepared according to a specific embodiment of the present invention will be described in detail.

₁₅

First, the hybrid supported metallocene catalyst of the present invention means a group on which at least one first metallocene compound and at least one second metallocene compound are supported. In addition, the hybrid supported metallocene catalyst of the present invention is characterized in that an aluminum-based promoter is supported together with the metallocene compound. Then, the metal-supported metallocene catalyst ₂₀ of the present invention may be further comprises a borate compound to the second co-catalyst. The present invention relates to a method for preparing a ₂₅ mixed supported metallocene catalyst, which can produce a polyolefin polymer having both improved apparent density and molecular weight distribution while maintaining high active catalyst properties. According to one embodiment of the invention, the step of supporting at least one first metallocene compound on the silica carrier; Contacting the silica carrier carrying the first metallocene compound with at least one aluminum-based promoter compound to support the aluminum-based promoter compound on the silica 30 carrier; And said 2019/156482 1 »（： 1 ^ 1 {2019/001535

Supporting at least one second metallocene compound on an aluminum-based promoter supported silica carrier; wherein the aluminum-based promoter compound is mixed on the silica carrier by a split dosing method at different temperatures. A method for preparing a supported metallocene catalyst may be provided. In other words, the present invention is to produce a mixed metal metallocene catalyst, silica to enable the control of the particle size of the polymer produced at the same time to implement the fine structure of the polymer for maximizing the active site generation and molecular weight distribution (¾ ■)) and comonomer distribution control The catalyst is divided into the carrier so that the promoter is distributed in a relatively large amount.

After the first split-input, the second split-input is carried out at a temperature of -5X: to 40X: to maintain high active catalyst properties while increasing polymer apparent density and wide molecular weight distribution to improve processability. Particularly, in the aluminum-based promoter compound, after supporting the first metallocene compound on the carrier carrier, 50 wt% to 90 wt% of the total amount of the promoter compound is about 100X: to about 150 First input from

Improved catalyst loading in the catalyst and improved polymer morphology (reduced fine powder generation) and apparent density and settling efficiency during slurry loop pilot process evaluation, resulting in higher activity and significantly increased ethylene load during process operation It is possible to improve the processability by increasing the molecular weight distribution, and can be used very effectively to produce polyolefins having a high apparent density and a wide molecular weight distribution. According to this method, the present invention can provide a supported metallocene catalyst having a specific parameter with respect to the content of time in the carrier. Preferably, the present invention comprises an outer layer comprising up to one third of the total diameter of the particle from each surface towards the center when the carrier catalyst particles are cut in cross section, and from one third point to the inner center of the particle. Containing the rest of the 2019/156482 1 »（： 1 ^ 1 {2019/001535

A silica carrier composed of an inner layer and having an aluminum-based promoter compound supported on the inside and the surface of the carrier; And two or more metallocene compounds supported on the silica carrier. For example, the city / element content ratio (% by weight) of the inner layer is 65% or more of the sand / element content ratio (% by weight) of the outer layer,

_It can provide ₅ supported metallocene catalysts. In particular, the present invention can implement a wide molecular weight distribution (_) with a high apparent density by first supporting at least one first metallocene compound on the silica carrier. In addition, the present invention can increase the supporting ratio of the city compared to the existing by high-temperature split injection of the aluminum promoter.

_{10 In} the hybrid supported metallocene catalyst according to the present invention, a large amount of aluminum-based promoter compound penetrates into the silica carrier and pores, and is chemically bonded, and a considerable amount of aluminum-based promoter compound is physically bonded to the surface. There is a combined feature. That is, conventionally, the aluminum-based promoter compound that penetrates into the carrier and is chemically bonded is small.

_15, but the present invention is to ensure that the co-catalyst is further supported on the inner layer than the prior art by a method for dividing when carrying the aluminum-based co-catalyst compound on the support. Therefore, the supported metallocene catalyst of the present invention contains a large amount of aluminum-based promoter compound in the inner layer in the composition consisting of the inner layer and the outer layer, thereby improving the apparent density compared to the existing and easy to control the catalyst activity Do.

20

 In the hybrid supported metallocene catalyst of the present invention having the above characteristics, when the silica carrier on which the aluminum-based promoter compound is supported is subjected to elemental analysis, the time / element content ratio (weight%) of the inner layer is determined by the time of the outer layer. / Element content ratio (65% or more of the weight, preferably 90% to 150%).

₂₅ which is aluminum-based means Hanyang plenty penetrate deeply to the inside layer portion of the crude aluminum silica support of the catalyst compound. Such a method for producing a hybrid supported metallocene catalyst according to the present invention comprises the steps of: supporting at least one first metallocene compound on a silica carrier; remind

30 One or more aluminum based silica carriers carrying the first metallocene compound Contacting the cocatalyst compound to support the aluminum-based cocatalyst compound on the silica carrier; And supporting at least one second metallocene compound on the aluminum carrier-supported silica carrier. Particularly, in the present invention, the first metallocene compound is first supported on a silica carrier, and then the aluminum-based cocatalyst is supported, and when the aluminum-based cocatalyst compound is supported, the temperature is changed from a high temperature to a low temperature and dividedly injected at different temperatures. Features are described below in more detail with respect to each step that can be included in the method of the present invention. First, the present invention may select a silica carrier having a morphology suitable for the Philips loop slurry process. The present invention optimizes the binding of alkylaluminoxanes, which are supported metallocene catalysts and promoters, by selectively controlling the amount of silanol and siloxane groups of the silica carrier through calcinations conditions. In addition, the chemical bond of the hydroxy key of the silica, that is, the 0H group and the co-catalyst (for example, a decrease in viscosity at high temperature of MA⑴ is allowed to penetrate to the inside, followed by a chemical reaction, and then physical adsorption occurs on the surface of the silica. In order to achieve this, the firing temperature of the silica can be carried out from the temperature at which the moisture disappears from the surface of the silica to the temperature range from which the hydroxyl group, that is, the 0H group, is completely disappeared from the surface of the silica. The firing conditions are preferably calcined at a temperature of about 100 ^° C. to about 700 ^° C. Through the firing, the water content of the silica carrier is preferably about 0.1 wt% to about 7 wt%. 2019/156482 1 »（： 1 ^ 1 {2019/001535

The inside of the silica carrier referred to in the present invention includes pores. In addition, unless stated otherwise throughout the present specification, the term "water content" of the carrier is defined as the percentage of the weight of water contained in the carrier relative to the total weight of the carrier. In addition, the support is indicated, a hydroxyl group at the time of about 0.5 on the surface of the support ₀₁ / for to about _{511 «1101} / I, preferably about 0.7 ^ ₀₁ ^ and about 2 _ _01, depending on the water content of the above-mentioned range May contain hydroxyl groups of seedlings. Such a carrier may be at least one member selected from the group consisting of silica, silica-alumina and silica-magnesia, preferably silica. In addition, any carrier that satisfies the above water content range can be used without limitation. On the other hand, the method for producing a hybrid supported metallocene catalyst according to the present invention includes the step of supporting at least one first metallocene compound on the silica carrier. In particular, the present invention implements a broad molecular weight distribution (■ å) by first supporting at least one first metallocene compound on the silica carrier to produce a feature of producing a polymer having excellent processability. In addition _, according to the present invention, since the catalytic activity is increased with high apparent density and wide molecular weight distribution through ethylene polymerization, the productivity of the polyolefin can be greatly improved. In the hybrid supported metallocene catalyst of the present invention, the first metallocene compound and the second metallocene compound are main catalyst components that can exhibit activity as a catalyst together with the aluminum-based promoter compound. The metallocene compound may be used as one or more first metallocene compounds and one or more second metallocene compounds without limitation to those conventional in the art. For example, the metallocene compound includes 1) a metallocene compound including a combination of non-bridged and Cp-based compounds; and 2) a combination of Si bridge Cp and Cp-based Si bridges. Metallocene compound, 3) Metallocene compound comprising a combination of C bridge Cp and Cp system, 4) Si bridge Cp or C bridge Cp (C bridge Mi and amine combination Metallocene compound comprising a, 5) Metallocene compound comprising a combination of ethylene bridge Cp and Cp system, 6) Metal containing a combination of phenylene bridge Cp and amine-based Rosene compound, 7) CC, Si-C, or metallocene compound containing Si-Si bridge, etc. can all be used. The Cp may be cyclopentadienyl, indenyl, fluorenyl, indenoindole (Inin), or the like, and the structure thereof is not limited. Also, the

Si-based bridges may include t-butoxy-nuclear substituents and similar structures, and in the case of indene structures, may include tetrahydro-indene structures. In addition, the metallocene compound of the present invention includes a low molecular metallocene compound (Cp-based) and a high molecular metallocene compound (eg, CGC type or ansa type). More specifically, as the first metallocene compound of the metallocene compound, for example, 1) a metallocene compound comprising a combination of non-bridged Cp and Cp-based, 2) Si bridge Cp ( A metallocene compound comprising a combination of Si bridge Cp) and a Cp system, 3) a metallocene compound comprising a combination of C bridge Cp and a Cp system, 5) an ethylene bridge Cp And metallocene compounds containing a combination of Cp-based and 7) CC, Si-C, or Si-Si bridges may be used. In addition, as the second metallocene compound of the metallocene compound, for example, 4) a metallocene compound including a combination of Si bridge Cp or C bridge Cp and an amine-based, or 6) One or more kinds of metallocene compounds including a combination of phenylene bridge Cp and amines may be used. 2019/156482 1 »（： 1 ^ 1 {2019/001535

For example, the metallocene compound may be at least one selected from the group consisting of Formulas 1 to 5 below:

[Formula 1]

In Chemical Formula 1,

 Is a Group 4 transition metal;

And ² are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1 -indenyl, and fluorenyl radicals They may be substituted with hydrocarbons of 1 to 20 carbon atoms;

And 0 are the same as or different from each other, and each independently hydrogen, alkyl of 01-020, 01-(: 10 alkoxy, alkoxyalkyl of 2-020, aryl of 06-020, 06- (aryloxy of 10), 02 to 020 alkenyl, 07 to 040 alkylaryl, 07 to 040 arylalkyl, 08 to 040 arylalkenyl, or 02 to (10: alkynyl, and

At least one of is not hydrogen;

 Each independently represents a halogen atom, alkyl of 01-020, alkenyl of 02-010, alkylaryl of 07-040, arylalkyl of 07-040, aryl of C6-020, substituted or unsubstituted 01-020 Alkylidene, substituted or unsubstituted amino group, alkylalkoxy of 02-020, or arylalkoxy of 07-040;

 Is 1 or 0;

[Formula 2]

In Chemical Formula 2,

M ² is a Group 4 transition metal; 2019/156482 1 »（： 1 ^ 1 {2019/001535

0 _? ³ and

Are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, 7-tetrahydro-1 -indenyl and fluorenyl radicals, which are 1 to Can be substituted with 20 hydrocarbons;

 11 ° and # are the same as or different from each other, and are each independently hydrogen, alkyl of 01-020, alkoxy of 01-(: 10, alkoxyalkyl of 01-020, aryl of C6-020, aryl of 06-10 (: 10) Oxy, 01-020 alkenyl, 01-040 alkylaryl, 07-040 arylalkyl, 08-040 arylalkenyl, or 01-10 (alkynyl;

 Each independently represents a halogen atom, 01-020 alkyl, 02-

(10: alkenyl, 07 to 40 alkylaryl, 01 to 040 arylalkyl, 06 to 020 aryl, substituted or unsubstituted 01 to 20 alkylidene, substituted or unsubstituted amino group, 02 to 020 Alkylalkoxy of; or arylalkoxy of 07 to 040;

Yo ¹ is _! ³ ^ with collar

Crosslink the ring, or a single! At least one or a combination of radicals comprising carbon, germanium, silicon, phosphorus or nitrogen atoms which crosslink the ring to ^ 1 ² ;

₀₁ is 1 or 0; [Formula 3]

 Cheating;

Dienyl, indenyl, 4, 5, 6, 7-tetrahydro-l-indenyl and fluorenyl radicals, which can be substituted with hydrocarbons having 1 to 20 carbon atoms;

Hydrogen, alkyl of 01-020, 01-(: 10 alkoxy, 02-020 alkoxyalkyl, 06-020 aryl, 06-(: 10 aryloxy, 02-020 alkenyl, (21-040) Alkylaryl, 07-040 arylalkyl, 08- 2019/156482 1 »（： 1 ^ 1 {2019/001535

Arylalkenyl of 40 or alkynyl of 02 to 00;

 Each independently represent a halogen atom, alkyl of 01-020, alkenyl of 02-010, alkylaryl of 040, arylalkyl of 01-040, aryl of 06-020, substituted or unsubstituted alkyl of 01-020 Lidene, a substituted or unsubstituted amino group, alkylalkoxy of 02-020, or arylalkoxy of 07-040;

# Is

One or more or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom-containing radicals which crosslink the ring and _1;

Any one selected from the group consisting of, wherein is independently 01 to 020 alkyl, aryl, substituted alkyl or substituted aryl,

[Formula 4]

In Chemical Formula 4,

II ¹ to ^ and the seedlings ^{1 '} to II ⁴ are the same as or different from each other, and each independently hydrogen, (the alkyl group of 1 to 020, the alkenyl group of 01 to 020, the aryl group of 06 to 020, the alkyl group of 07 to 020) An aryl group, an arylalkyl group of 07 to 020, or an amine group of 01 to 020, and adjacent to the above-mentioned II ¹ to II ⁴ and seedlings ^{1 '} to ^4'

Two or more may be linked to each other to form one or more aliphatic rings, aromatic rings, or heterocycles;

S and are the same as or different from each other, and each independently hydrogen, an alkyl group of 01 to 020, a cycloalkyl group of 03 to 020, (the alkoxy group of 1 to 020, 2019/156482 1 »（： 1 ^ 1 {2019/001535

06-020 aryl groups, 06-010 aryloxy groups, 02-020 alkenyl groups, 07-040 alkylaryl groups, or 07-040 arylalkyl groups;

 Is an alkyl group of 02 to 020, a cycloalkylene group of 03 to 020, an arylten group of 06 to 020, an alkyl arylene group of 07 to 040, or an arylalkylene group of 1 to 040;

M ⁴ is a Group 4 transition metal;

 公 and are the same as or different from each other, and each independently halogen, 01-020 alkyl group, 02-020 alkenyl group, 06-020 aryl group, nitro group, amido group, (： 1-020 alkylsilyl group, (The 1-020 alkoxy group, 02-020 ester group, or 01-020 sulfonate group;

[Formula 5]

In Chemical Formula 5,

II ⁵ and 11 ^{5 '} are each independently hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, silyl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, carbon atoms A metalloid of a Group 4 metal substituted with 7 to 20 arylalkyl or hydrocarbyl; The II ⁵ and II ^{5 ′} or two parent ^{5 ′} may be linked to an alkylidine comprising alkyl having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms to form a ring;

II ⁶ are each independently hydrogen, a halogen atom, an aryl, a carbon number of 1 to 20 carbon atoms alkyl, C2 to C20 alkenyl, C6 to C20 aryl, C7 to C20 alkylaryl, C7 to C20 of the Alkoxy of 1 to 20, aryloxy or amido of 6 to 20 carbon atoms; Two or more seedlings ⁶ of the II ⁶ may be linked to each other to form an aliphatic ring or an aromatic ring; CY ¹ is a substituted or unsubstituted aliphatic or aromatic ring, and the substituent group substituted in CY ¹ is a halogen atom, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and having 7 to 7 carbon atoms. 20 alkylaryl, arylalkyl having 7 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, and amido; when the substituents are plural, two or more substituents from the substituents are connected to each other. Can form aliphatic or aromatic rings;

M ⁵ is a Group 4 transition metal;

Q ³ and Q ⁴ are each independently halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, and carbon atoms. Alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms or alkylidene having 1 to 20 carbon atoms. In this case, the metallocene compound including a combination of the non-bridge Cp and the Cp-based may include the compound represented by Chemical Formula 1. The metal bridgene compound containing a combination of Si bridge Cp (metal bridgeene compound containing a combination of Si bridge and Cp system and C bridge Cp (C bridge Cp) and Cp system, the compound represented by the formula (2) In Formula 2, the Cp ³ R ^c ring and the Cp ⁴ R ^d ring may be cross-linked, or one Cp ⁴ R ^d ring may be cross-linked with M ² to carbon, germanium, silicon, phosphorus of B ¹ . Or a nitrogen atom A metallocene compound including a combination of the Si bridge Cp or the C bridge Cp and an amine may include a compound represented by Chemical Formula 3. The metallocene compound including a combination of ethylene bridge Cp and Cp-based may include a compound represented by Chemical Formula 4. Crosslinking two cyclopentadienyl groups in the formula (4)

Germanium, silicon, phosphorus or nitrogen atoms are distinguished. In formula (4), 02 to 020 alkylene group, 03 to 020 cycloalkylene group, 03 to 020 arylene group, 06 to 020 arylene group, 07 to 040 alkyl arylene group, or The arylalkyltene group of 07 to 040 represents a divalent substituent in the form of further removing a hydrogen atom from each alkyl group, cycloalkyl group, aryl group, alkylaryl group, arylalkyl group. The metallocene compound including a combination of the phenylene bridge Cp and an amine system may include a compound represented by Chemical Formula 5. In addition, hydrocarbyl, as defined in Formula 5, is a monovalent group in which hydrogen atoms are removed from hydrocarbons, and includes ethyl, phenyl, and the like. In addition, the metalloid is a metalloid, an element showing intermediate properties between metal and nonmetal, and includes arsenic, boron, silicon, tellurium, and the like. Specifically, in the hybrid supported metallocene catalyst of the present invention, the first metallocene compound may be a compound represented by Formula 1, 2, or 4, and specifically, may be a compound represented by Formula 1. In addition, the second metallocene compound in the hybrid supported metallocene catalyst may be a compound represented by Formulas 3 and 5, and specifically, may be a compound represented by Formula 3. According to an embodiment of the present invention, specific examples of the compound represented by Chemical Formula 1 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto. \ ¥ 0 2019/156482 1 1710 2019/001535

Specific examples of the compound represented by Chemical Formula 2 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto. 2019/156482 1 »（： 1/10 公 019/001535

According to one embodiment of the present invention, specific examples of the compound represented by Chemical Formula 3 include a compound represented by one of the following structural formulas, but the present invention is not limited thereto. 2019/156482 1 »（： 1 ^ 1 {2019/001535

According to an embodiment of the present invention, ¥ of Formula 4 is from 02 to

020 is an alkylene group or an ethylene group, and minutes are each independently hydrogen, 01

It may be halogen, but is not limited to this. In addition, specific examples of the compound represented by Chemical Formula 4 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

2019/156482 1 »（： 1/10 公 019/001535

In addition, the compound represented by Chemical Formula 5 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

2019/156482 1 »（： 1 ^ 1 {2019/001535

In the above formula, each II ⁷ is independently hydrogen or methyl; ( ⁵ and silver may each independently be methyl, dimethyl amido or chloride. The metallocene compound represented by Chemical Formula 5 is structurally connected to a metal site by a cyclopentadienyl ligand introduced with an amido group linked to a phenylene bridge in a ring form.

The angle is narrow and the 0 ³ ^ ⁵ -0 ⁴ angle to which the monomer approaches can be kept wide. In the hybrid supported metallocene catalyst of the present invention, the substituents of Chemical Formulas 1 to 5 are more specifically described as follows. The alkyl group of 01 to 020 includes a linear or branched alkyl group, and specifically, methyl group, ethyl group, propyl group, isopropyl group, ₁₁ -butyl group, butyl group, pentyl group, nuclear group, heptyl group, octyl group Etc., but is not limited to this. The alkenyl group of 02 to 020 includes a straight or branched alkenyl group, and specifically includes an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like, but is not limited thereto. The alkylene group of 02 to 020 includes a linear or branched alkylene group, and specifically, may include an ethylene group, a propylten group, a butylten group, a pentylene group, a nuclear styrene group, a heptylene group, an octylene group, and the like. It is not limited only. Specific examples of the 03 to 020 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclonuxyl group, a cycloheptyl group, and a cyclooctyl group, but are not limited thereto. 2019/156482 1 »（： 1 ^ 1 {2019/001535

Specific examples of the 03 to 020 cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentyltene group, a cyclonuxylene group, a cycloheptylene group, and a cyclooctylene group, but are not limited thereto. The aryl group of 06 to 020 includes a monocyclic or condensed aryl group, and specifically includes a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, and a fluorenyl group, but is not limited thereto. The arylene group of 06 to 020 includes a monocyclic or condensed aryl group, and specifically includes a phenylene group, a biphenylene group, a naphthylene group, a phenanthrenylene group, a fluorenylene group, and the like. It is not. Examples of 01 to 020 alkoxy groups include, but are not limited to, methoxy, ethoxy, phenyloxy and cyclonucleooxy groups. The alkoxyalkyl group of 02 to 020 is a functional group in which at least one hydrogen of an alkyl group is substituted with an alkoxy group, and specifically, a methoxymethyl group, a methoxyethyl group _, an ethoxymethyl group _{, a {30} -propoxymethyl group, ᅵ _30- Propoxyethyl group ，

Alkoxyalkyl groups such as 1 ₆₁ 1; -butoxymethyl group,!; -Butoxyethyl group, and 1 _61.! ; Or an aryloxyalkyl group such as a phenoxynucleosil group, but is not limited thereto. The alkyl silyl group of 01 to 020 or the alkoxysilyl group of 01 to 020 is a functional group in which 1 to 3 hydrogens of ¾ are substituted with 1 to 3 alkyl groups or alkoxy groups as described above, and specifically methylsilyl group, dimethyl Alkylsilyl groups such as silyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group or dimethylpropylsilyl group; Alkoxy silyl groups, such as a methoxy silyl group, a dimethoxy silyl group, a trimethoxy silyl group, or a dimethoxyethoxy silyl group; Alkoxyalkylsilyl groups _{, such} as a methoxy dimethyl silyl group, a diethoxy methyl silyl group, or a dimethoxy propyl silyl group, are mentioned, but it is not limited to this. 2019/156482 1 »（： 1 ^ 1 {2019/001535

The silylalkyl group of 01 to 020 is a functional group in which one or more hydrogens of the alkyl group as described above are substituted with a silyl group, and specific examples thereof include-(: ¾-¾, methylsilylmethyl group or dimethylethoxysilylpropyl group, and the like. ， Not limited to this. The halogen word) may be fluorine 00, chlorine (II), bromine () or iodine (I). The sulfonate group-0-ssaet _2-yo ^'seedlings in the structure ^"may be an alkyl group of 01 to 020. Specifically, the 01 to 020 sulfonate group may include a methanesulfonate group or a phenylsulfonate group, but is not limited thereto. The ester group -0- ¥ ^"our structure ^{of" "is} 01 to 019 may be an alkyl group, a substituent of the type removing a hydrogen atom from the carboxylic acid of C2 to 020. In particular, 02 to 020 ester group methylate Group, ethylate group, propylate group, pivalate group, etc., but are not limited thereto .. The above-mentioned substituents are optionally a hydroxy group within the range exhibiting the same or similar effects as the desired effect; Halogen; alkyl group or alkenyl group, aryl group, alkoxy group; alkyl group or alkenyl group, aryl group, alkoxy group; silyl group; alkylsilyl group or alkoxysilyl containing at least one hetero atom of group 14 to 16 hetero atoms Group, phosphine group, phosphide group, sulfonate group, and sulfone group. The other metals include titanium (), zirconium () and hafnium (), but this is not limited. 2019/156482 1 »（： 1 ^ 1 {2019/001535

According to an embodiment of the present invention, the metallocene compound may be synthesized by applying known reactions. Specifically, each ligand compound may be prepared, and then a metal precursor compound may be added to perform metallization ( ₁₁₁ 1 ₀₁₁ ), but the present invention is not limited thereto. For detailed synthesis methods, see Examples. . On the other hand, the present invention is characterized in that the aluminum-based cocatalyst compound is added at high temperature after the first support of the at least one first metallocene compound on the silica carrier. The supporting step of the first metallocene compound may be performed by mixing and stirring the silica carrier and the metallocene compound in the presence of a solvent. At this time, the amount of the first metallocene compound supported on the silica carrier by the step is about 0.01 ^ ₀ 1 ^ to about 1 _ ₀ 1 / sugar, or about 0.1 ₁₁₁₀ 1 / sugar based on the carrier 1 About 1 _1111110 1 / _dragon . That is, in view of the contribution effect of the catalytic activity by the first metallocene compound, it is preferable to fall within the above-described supported amount range. The temperature condition in the supporting step of the first metallocene compound is not particularly limited. On the other hand, after the above process, the method for producing a hybrid supported metallocene catalyst of the present invention, by contacting the silica carrier carrying the first metallocene compound with at least one aluminum-based promoter compound, Sequentially supporting the aluminum gray catalyst compound. 2019/156482 1 »（： 1 ^ 1 {2019/001535

In particular, the present invention provides a low temperature of about -5 X: to about 40 I: at a high temperature of about 100 V to about 150 X: when the aluminum-based promoter compound is supported on a silica carrier carrying the first metallocene compound. While changing the temperature, there is a feature of split injection at different temperatures. That is, the aluminum-based cocatalyst compound is about a part of the total amount

May include Thus, according to one preferred embodiment of the present invention, the aluminum-based promoter compound is a part of the total amount, that is, about 50% to 90% by weight, or about 60% to 90% by weight of about 100%

To about 150 X], or about

110 I: first dose at a temperature of from about 130 kPa, the remainder of the total dose, ie from about 50% to 10% by weight, or from about 40% to about

Provided is a method for preparing a hybrid supported metallocene catalyst supported on a silica carrier by a split dosing method in which 10 wt% is secondaryly injected at a temperature of about −5 V to about 40 ×: or about 0 to about 40. In addition, according to a preferred embodiment of the present invention, the silica carrier on which the aluminum-based promoter compound is loaded is about 60 wt% to about 90 of the total amount of alkylaluminoxane added at a high temperature of about 110 X: to about 130 I: Weight percent

The remaining alkylaluminoxane, such as from about 40% to about 10% by weight of the alkylaluminoxane, may be obtained by carrying out a secondary charge on a silica carrier to carry out the post-reaction. 2019/156482 1 »（： 1 ^ 1 {2019/001535

More specifically, in the present invention, the silica carrier on which the first metallocene compound obtained in the above step is supported is contacted with an aluminum compound as a cocatalyst component. At this time, the contact method of the present invention by contacting the aluminum-based cocatalyst compound by split injection into the silica carrier in the secondary as described above, as described above, a larger amount of aluminum-based cocatalyst compound in the silica carrier as described above It is to be penetrated and also to carry a considerable amount of aluminum-based promoter compound on the surface. According to this method, an aluminum-based promoter compound provides a silica carrier composed of an inner layer and an outer layer surrounding the silica carrier supported on the inside and the surface thereof. In order to increase the content of the cocatalyst in the silica, the chemical bond ((土_{3 3} ± _1016111 :)) predominates, lowers the viscosity of the reactants, and the alkyl at high temperature is easy to diffuse to the pores of the silica. By contacting aluminoxane and silica carrier in advance and additionally contacting alkylaluminoxane at low temperature, the cocatalyst component is supported on the silica surface by physical adhesion (1) 1173 31 3 (ie! 011). According to the present invention, the apparent density and the catalytic activity of the polymer can be controlled not only by the amount of alkylaluminoxane and the contact temperature, but also by the injection method.The supporting conditions of the alkylaluminoxane are, as described above, at least two alkylaluminoxanes. Split injection is used at high and low temperatures more than one time, for example, aluminum-based co-solvent compounds are divided twice.

In the range of 40, the alkylaluminoxane is supported while being dividedly added to carry out post-reaction. In addition, the aluminum-based cocatalyst compound is first supported by adding about 50% by weight to about 90% by weight, or about 60% by weight to about 90% by weight of the total amount of alkylaluminoxane in the first injection. Add the remaining balance to the secondary. 2019/156482 1 »（： 1 ^ 1 {2019/001535

At this time, if the aluminum-based promoter compound, which is the promoter, is added at once without being divided into, the aluminum-based promoter compound is unevenly supported on the carrier, and aluminum is excessively present on the surface of the carrier. On the other hand, metallocene compounds with small molecules are uniformly supported inside and outside. Therefore, since the aluminum-based cocatalyst compound is collectively added, the metallocene compound supported therein cannot be activated so that the total catalyst activity is reduced, and as a result, the polymerization by the catalyst activated only on the outside proceeds, resulting in low apparent density. There is a problem. In particular, even when the cocatalyst is separately added as described above, the primary

When carried out, it is possible to significantly increase the content supported in the final catalyst relative to the input content. That is, as described above, even if the supporting process is carried out using the same amount of the promoter by supporting the split at high temperature, the amount of the promoter actually supported on the catalyst is much higher, and the supporting efficiency is higher. Can be.

It is a cocatalyst component which assists the activity of a 1st metallocene compound and a 2nd metallocene compound. The step may be carried out by mixing the silica carrier and the alkylaluminoxane in the presence or absence of a solvent and reacting with stirring. Here, the aluminum-based promoter compound may be represented by the following formula (6), for example.

 [Formula 6]

-(Show 1 (11 ⁹ )-(0) 山 -11 ^{1 ()} 2019/156482 1 »（： 1 ^ 1 {2019/001535

In Chemical Formula 6,

II ⁸ , II ⁹ , and 11 ^{1 ()} are the same as or different from each other, and are each independently hydrogen, halogen,

A hydrocarbyl group of 020 to 020, or a C \ 020 hydrocarbyl group substituted with halogen;

 1 is 0 or 1;

X is an integer of 2 or more. The aluminum-based cocatalyst compound of Chemical Formula 6 may be an alkylaluminoxane compound, a trialkylaluminum compound, etc., in which a repeating unit is bonded in a linear, circular, or reticular form. In addition, the alkyl group bonded to aluminum in the aluminum-based cocatalyst compound may be each consisting of 1 to 20 carbon atoms or 1 to 10 carbon atoms. Specifically, specific examples of such aluminum-based promoter compounds include alkyl aluminoxane compounds such as methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane; Or trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trinuclear silaluminum, trioctatalaluminum or isoprenylaluminum. The amount of the aluminum-based promoter compound supported on the silica carrier by the above step is about 5 ₁ p ₁₀₁ to about 15 ^ ₁₀₁ / yo, or about 8 ₁ when ₀₁ / yo to about 13 11 ^ It can be 101 / day. That is, within the supported amount range, the aluminum-based promoter compound is supported on the silica carrier by dividing at a high temperature and a low temperature, so that the above-described pre- and post-reaction of the aluminum-based promoter compound can be performed. In this case, a solvent may be used to induce a smooth contact reaction between the carrier and the aluminum-based promoter compound, or may be reacted without the solvent. The solvent includes aliphatic hydrocarbons such as nucleic acids, pentane and heptane; Aromatic hydrocarbons such as toluene, benzene; Hydrocarbons substituted with chlorine atoms such as dichloromethane; Ethers such as diethyl ether and tetrahydrofuran 奸; Most organic solvents such as acetone and ethyl acetate can be used. 5 Preferably, nucleic acid, heptane, toluene or dichloromethane may be used as the solvent. In this process, the present invention can provide a silica carrier in which a greater amount of aluminum-based promoter compound penetrates into the inside of the silica carrier and a significant amount of ₁₀ aluminum-based promoter compound is bound to the outside thereof. On the other hand _, the method for producing a supported metallocene catalyst according to the present invention includes the step of supporting at least one second metallocene compound on a silica carrier carrying the aluminum-based promoter compound.

₁₅

The present invention is supported by the above method according to the reaction conditions of each metallocene compound by supporting at least one second metallocene compound on a silica carrier in which the first metallocene compound and the aluminum-based promoter compound are separately supported. The interaction with the promoter is optimized to allow the catalyst properties to be adjusted. As metallocene catalyst ₂₀ produced supported metal in this way using a SEM / EDS analysis examining the inside depth of the profile carrier of the catalyst (depth prof i le), of silica of an aluminum-based co-catalyst compound, confirmed that the external loading is controlled can do. The second metallocene compound may be used at least one selected from the group consisting of ₂₅ to ₂₅ as described above. The step can be carried out by mixing the carrier and the second metallocene compound in the presence of a solvent and reacting with stirring. 2019/156482 1 »（： 1 ^ 1 {2019/001535

At this time, the supporting amount of the second metallocene compound supported on the silica carrier by the above step is about 0.01 _1111110 1 / yaw about 1 _{■ 0} 1 / seedling, or about 0.1 minus ₀ 1 八 to about 1 based on the carrier 1 yaw _ ₀ 1 / can be for. That is, in consideration of the contribution effect of the catalytic activity by the metallocene compound, it is preferable to fall within the above-described supporting amount range. In addition, the temperature condition in the supporting step of the second metallocene compound is not particularly limited. On the other hand, in the method for producing the hybrid supported metallocene catalyst of the present invention, the silica carrier on which the first metallocene compound is supported is brought into contact with at least one aluminum-based promoter compound to contact the silica carrier with the aluminum-based promoter compound. After supporting, the second metallocene compound is sequentially supported, whereby polyolefin having a wide molecular weight distribution with apparent density can be produced very effectively. In particular, the mixed molar ratio of the first metallocene compound and the second metallocene compound may be about 1: 0.5 to 1: 2.5 or about 1: 1 to 1: 1.5. On the other hand, the present invention can further support a borate compound as the second catalyst. That is, the present invention is one or more first metallocene compounds, one or more aluminum-based promoter compounds, and one or more The method may further include supporting a borate compound as a second cocatalyst on a silica carrier on which the second metallocene compound is supported. Therefore, according to one preferred embodiment of the invention, the carrier is supported by at least one low 11 metallocene compound, an aluminum-based promoter as a first promoter, and a borate compound as a second promoter, The second metallocene compound may be supported. Alternatively, according to another preferred embodiment of the present invention, an aluminum-based cocatalyst as one or more first metallocene compounds and a first cocatalyst on a carrier 2019/156482 1 »（： 1 ^ 1 {2019/001535

The compound may be supported, at least one second metallocene compound may be supported, and the borate compound may be supported as a low 12 cocatalyst. When the second cocatalyst is included in the supported metallocene catalyst, the polymerization activity of the final prepared catalyst may be improved. The second cocatalyst, the borate compound, may include a borate compound in the form of a trisubstituted ammonium salt, a borate compound in the form of a dialkyl ammonium salt, or a borate compound in the form of a trisubstituted phosphonium salt. Specific examples of such a second cocatalyst include trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri-butyl) ammonium tetraphenylborate, Methyltetracyclocyclodecylammonium tetraphenylborate,

Tetraphenylborate, diethylanilium tetraphenylborate,

Trimethylaninium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethyl Ammonium Tetrakis (pentafluorophenyl) borate, Tripropylammonium Tetrakis (pentafluorophenyl) borate, Tri-butylammonium Tetrakis (pentafluorophenyl) borate, Tri (tert-butyl) ammoniumtetrakis (Pentafluorophenyl) borate, 刀 -dimethylaninium tetrakis (pentafluorophenyl) borate, -diethylanilium tetrakis (pentafluorophenyl) borate,

Trimethylanilium) tetrakis (pentafluorophenyl) boride trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluoro Lophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,

Tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilium 2019/156482 1 »（： 1 ^ 1 {2019/001535

Tetrakis (2,3,4,6-tetrafluorophenyl) borate, or N, N-dimethyl- (2,4,6-trimethylaninynium) tetrakis (2,3,4,6-tetrafluoro Borate compounds in the form of trisubstituted ammonium salts such as phenyl) borate; Borate type in the form of dialkyl ammonium salt, such as dioctadecyl ammonium tetrakis (pentafluorophenyl) borate, ditetradecyl ammonium tetrakis (pentafluorophenyl) borate, or dicyclonuclear ammonium tetrakis (pentafluorophenyl) borate compound; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) Borate compounds in the form of trisubstituted phosphonium salts such as borate; and the like. In addition, the borate compound may be supported by a content of about ₀ to about 1 _{11111101 by} subtracting about 0.01 based on the use of silica carrier 1. In the case of using a borate compound as a second catalyst in the method of the present invention, the supporting order is not particularly limited. For example, according to the present invention, a borate compound may be finally supported on a silica carrier after supporting one or more second metallocene compounds. In addition, the present invention optionally provides a non-aluminum-based promoter compound to be a silica carrier. After supporting it, it can carry out in order of supporting a borate type compound, and then supporting one or more metallocene compounds. On the other hand, according to another embodiment of the present invention, there is provided a method for producing a polyolefin comprising the step of polymerizing the olefin monomer in the presence of the supported metallocene catalyst. The method for producing the polyolefin may include preparing the hybrid supported metallocene catalyst; And polymerizing the olefinic monomers in the presence of the catalyst. The supported metallocene catalyst according to the present invention itself is subjected to a polymerization reaction. Can be used. In addition, the supported metallocene catalyst may be prepared by using a prepolymerized catalyst by contacting with an olefinic monomer. For example, the supported metallocene catalyst may be separately contacted with an olefinic monomer such as ethylene propylene 1-butene, 1-nuxene, 1-octene, and the like. It can also be prepared by using a prepolymerized catalyst. In addition, the supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms (for example, pentane, nucleic acid, heptane, nonanedecane and isomers thereof) and an aromatic hydrocarbon solvent such as toluene benzene, and chlorine such as dichloromethane chlorobenzene. Dilution with an atom substituted hydrocarbon solvent or the like may be carried out to the reactor. At this time, by adding a small amount of alkylaluminum to the solvent, it is preferable to use after removing a small amount of water or air which can act as a catalyst poison (catalyst poi son). The polymerization reaction may be carried out by homopolymerization with one olefinic monomer or copolymerization with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor gas phase reactor, or a solution reactor.

1 _¾ can be performed at /. In this case, the olefin monomer may be selected and used according to the type of the deliolefin to be prepared, preferably ethylene, propylene, 1-butene 1-pentene 4 -methyl- 1-pentene, 1 -nucleene 1 -heptene 1 -octene ， 1 -Desen ， 1 -Undesen ， 1- 2019/156482 1 »（： 1 ^ 1 {2019/001535

Dodecene, 1-tetradecene, 1-nuxadecene, 1-aitosen, norbornene, norbonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1 One or more olefinic monomers selected from the group consisting of -5-pentadiene, 1,6-nuxadiene, styrene, alpha-methylstyrene, divinylbenzene and 3 -chloromethylstyrene can be used. Specifically, the polyolefin may be polyethylene which is an ethylene homopolymer, or may be a binary copolymer of ethylene-1-nuxene. Polyolefins prepared according to the method provide the effect of high apparent density, broad molecular weight distribution, and settling efficiency while maintaining high activity equal to or higher than the existing. Specifically, the polyolefin has an apparent density of about 0.38 yong / ₁ kPa or about 0.38 yo / 此 about 0.8 sugar or about 0.4 g / mL or more or about 0.4

When the polymerization reaction is carried out in a loop slurry reactor, the polyolefin has an apparent density of about 0.47 or more or about 0.47 or about 0.8 to about 0.8 or about 0.49 g / x or about 0.49 g or more. / mL to about 0.8 palaces per square foot. The apparent density of the polyolefin may vary depending on the density, particle size, and particle size distribution of the polyolefin. The larger the particle size distribution, the higher the apparent density. However, the larger the particle size distribution, the larger the amount of small particles (fine powders), and the fine powders do not settle well in the solvent during polymerization, thereby lowering the settling efficiency. Therefore, when comparing the apparent densities of polyolefins, the particle size distribution should also be viewed, rather than the absolute value of the apparent density. In addition, when the particle size distribution is narrow, that is, when the particle size is uniform, the apparent density of the polyolefin may appear lower as the particle size is larger. However, the hybrid supported catalyst of the present invention, even if the activity is equal or more, 2019/156482 1 »（： 1 ^ 1 {2019/001535

The particle size is large and the distribution is narrow, and the apparent density increases, which has the advantage. This means that the particles of the resulting polymer are densely produced, thereby improving the settling efficiency when copolymers of the same density are produced through copolymerization in actual continuous processes, and the ethylene consumption per hour (polymer production) is about 15% or more, Or about 17.5% or more, or about 20% or more, thereby increasing overall productivity. Specifically, in the particle size distribution analysis of the polyolefin, the particle size is 180! The fine powder content below may be less than about 0.1% based on the total weight of the total polyolefin, and may preferably appear to be about 0.01% or less at all. In addition, when the particle size of the polyolefin is less than 300 ^ may be about 1.2% or less or about 0 to 1.2%, or about 1.0% or less or about 0.2% to 1.0%. In addition, the particle size of the polyolefin in excess of 300 _{/ /} 500 쌘! If less than

About 19.2, or about 16 ¾ to about 18.5%. In addition, when the particle size of the polyolefin exceeds 500 _ may be about 75 \ vtro or more, or about 80% or more. In addition, when the particle size of the polyolefin exceeds 850 may be about 20% or more, or about 25% or more. In particular, the sum of the content ranges of the respective particle sizes in the particle size distribution of the polyolefin may not exceed 100%. The particle size distribution analysis of the polyethylene can be measured using a sieve that can separate the polymer by particle size, and the specific measuring method is as described in the ethylene homopolymerization-related polymerization preparation example described below. For example, the polyolefin has a fine powder content of 0 or less with a particle size of 180 ^ or less based on the total weight of total polyolefins, and a particle size of about 0.4 or less for a particle size of more than 180_ and about 0.4.

To about 0.9%, particle size of 300 _/ over 500 _{/ up} to about 18.1% to about 18.1%, particle size above 500] of about 850%! Less than about 49.0 to 55.0 %, Particle size exceeding 850 _ about 27.9% To about 32.3 _\ %. As an example, the apparent density (BD) of the polyolefin may be measured based on ASTM D 1895 Method A. Specifically, the bulk density (BD) of the polyolefin is determined by filling a polyolefin in a 100 mL volume (eg, SUS container) and measuring the weight (g) of the polyolefin, from which the weight per unit volume (g / mL) This can be a value. On the other hand, the polyolefin may have a wide molecular weight distribution with the high apparent density and the optimized particle size distribution as described above. Specifically, the polyolefin ions molecular weight distribution (Mw / Mn) may be about 4.0 or more or about 4.0 to about 8.0, or about 4.2 or more or about 4.2 to about 7.0. For example, the molecular weight distribution (MTO, polydispersity index) is measured by gel permeation chromatography (GPC, gel permeation chromatography, Water Company) to measure the weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene, The weight average molecular weight can be divided by the number average molecular weight to calculate the weight. Specifically, Water Permeation Chromatography (GPC) apparatus using a Waters PL-GPC220 device, Polymer Laboratories PLgel MIX-B 300 mm length column can be used. At this time, the measurement temperature is 160 ^° C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) can be used as a solvent, the flow rate can be applied to l mL / min. Preprocessed by dissolving in trichlorobenzene (1,2,4- Tri chlorobenzene) containing BHT 0.0125% for 10 hours using GPC analysis instrument (PL-GP220) for 10 hours, and then prepared at a concentration of 10 mg / 10mL , 200 uL. Assay curves formed using polystyrene standards can be used to derive the values of Mw and Mn. The weight average molecular weight of the polystyrene standard specimen is 2000 / ₁₁₁₀ 1, 10000 / / 1, 30000 / / 1, 70000 yo / ₁₁₁₀ 1, 200000 yo / ₁₁₁₀ 1, 700000 yo / 1, 2000000 yo / ₀ 1, 4000000 / / 1, 10000000 / Nine kinds are available. The polyolefin may exhibit a weight average molecular weight of about 50000 g / mol to about 250000 g / mol. The polyolefin can also have a density value measured by ASTM 1505 from about 0.920 g / cm ³ to about 0.950 g / cm ³ , preferably from about 0.930 g / cm ³ to about 0.940 g 八: m ³ . In addition, the polyolefin may have a settling efficiency of about 65% to about 80%, or about 67% to about 80%, which is defined by Equation 1 below.

 [Calculation 1]

 Settling efficiency (%) = amount of ethylene used 八: amount of ethylene used + solvent content.

On the other hand, the hybrid supported catalyst according to the present invention can not only produce a polyolefin with improved apparent density, wide molecular weight distribution, and settling efficiency as described above, but also maintain high catalytic activity. Specifically, in the polyolefin polymerization process, the catalytic activity may be measured by dividing the weight of polyethylene produced through the polymerization process by 0 _¾ ) by the weight of the supported catalyst used in the polymerization process ( _§ ), wherein the catalytic activity is about 10

(Polyolefin) / _§ (catalyst) to about 25 (polyolefin) / _¾ (catalyst), or about 10.8

(Polyolefin) / _§ (catalyst) or more (polyolefin) / _§ (catalyst) to about 23

Can be. In particular, when the hybrid supported catalyst as described above is applied to the loop slurry reactor to perform the polymerization reaction, Catalytic activity is at least about 11 (polyolefin) / _§ (catalyst) or about 11

(Polyolefin) / solvent (catalyst), or about 11.5

(Polyolefin) / yo (catalyst) to about (polyolefin) / _§ (catalyst). The method for measuring the catalytic activity is as described in the ethylene homopolymerization related polymerization preparation example described later, and the description for the specific measurement method is omitted.

【Effects of the Invention】

According to the present invention, the supported catalyst co-catalyst loading rate is improved, the morphology (reduced _fine powder reduction) and apparent density of the produced polymer is increased while maintaining the high catalytic activity, and the settling ( ₃ 1: 11 _1¾ ) efficiency is improved. The molecular weight distribution can be used very effectively to produce a polyolefin with improved processability. [Form for implementation of the invention]

 The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples. <Example>

 <Synthesis example of metallocene compound>

 Synthesis Example 1 First Metallocene Compound

Using 6-chlorohexanol, Tetrahedron Lett. T-Butyl-0- (CH ₂ ) _6- Cl # was prepared by the method described in 2951 (1988)), and Na-Cp was reacted to obtain t-Buty 卜 0- (C¾) _6- C ₅ H _5. Yield 60%, bp 80 ^° C /

0.1 mmHg）. In addition, dissolve t-Butyl-0- (CH ₂ ) ₆ -C ₅ H ₅ in THF at -78 ^° C, add normal butylium (n-BuLi) slowly, and then warm to room temperature, 8 hours Reacted. The solution was again brought to ZrCl ₄ (THF) ₂ (1.70 g, at -78 ^° C, 4.50_ol) / THF (30m £) to the suspension (suspension) solution of the pre-synthesized lithium salt (li thium salt) solution was added slowly and further reacted for 6 hours at room temperature. All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of a hexane solvent. The filtered solution was dried in vacuo and nucleic acid was added to induce precipitate at low temperature (-20 ° C). The precipitate obtained was filtered at low temperature to give a bis (3- (6- (tert-butoxy) nucleosil) cyclopenta-2,4-diene-1-yl) -zirconium dichloride [(Bis (3- ( 6- (tert-butoxy) hexyl) cyclopenta-2,4-dien-1 -yl) -zirconiumdi chloride) and tBu-O-CCH ^ -CsH ^ ZrCy compounds were obtained (yield)

92%).

0001 ₃₎ ： 6.28 (I = 2.6 ¾, 2 11) ， 6. 19 0 :， I =

2.6 ¾, 2 ratio, 3.31 (1 ;; 6.6 ¾, 2, 2.62 (1, 1 = 8 ¾), 1.7-1.3 (8 11), 1. 17 (9.

¹³ 0 ■ (0) _3): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00. Synthesis Example 2 Second Metallocene Compound

Mg (s) for 50 at room temperature was added to a 10 L reactor, followed by 300 mL of THF. After adding _0.5 g of 1 ₂ , the reactor temperature was maintained at 50 ° C. After the reactor temperature stabilized, 250 6-t-butoxynuxyl chloride (6-t-buthoxyhexyl chloride) was added to the reactor at a rate of 5 mL / min using a feeding pump. It was observed that the reactor temperature rose about 4 to 5 ^° C. with the addition of 6-t-butoxynucleus chloride. The mixture was stirred for 12 hours while adding 6-t_butoxynuxyl chloride. After 12 hours, a black reaction solution was obtained. 2 mL of the resulting black solution was taken and water was added thereto to obtain an organic layer. 6-t-butoxynucleic acid (6-t-buthoxyhexane) was confirmed by 1 H-NMR. From the 6-t-butoxynucleic acid, it was found that the Gr inganrd reaction proceeded well. Thus 6-t-butoxynuclear magnesium Chloride (6-t-buthoxyhexyl magnesium chloride) was synthesized.

500 g of MeSiCls and 1 L of THF were added to the reactor and the reactor temperature was cooled to -20 ° C. 560 g of the synthesized 6-t-butoxynucleosil magnesium chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. After feeding the Grignard reagent, the reaction mixture was stirred for 12 hours while slowly raising the temperature of the reactor. After 12 hours of reaction, white MgCl ₂ salt was produced. 4 L of nucleic acid was added to remove the salt through a labyrinth (l abdor i) to obtain a filter solution. After the obtained filter solution was added to the reactor, the nucleic acid was removed at 70 ° C to obtain a pale yellow liquid. Obtained liquid 1H-

NMR confirmed that the desired compound was methyl (6-t-butoxy hexyl) dichlorosilane {Methyl (6-t-buthoxy hexyl) dichlorochloroamine.

1 H-NMR (CDC13): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H) tetramethyl 1.2 mol cyclopentadiene (tetramethyl cyc lopentadiene)

(150 g) and 2.4 L of THF were added to the reactor and the reactor temperature was cooled to -20 ° C. The reactor was added at a rate of 5 mL / min using an n-BuLi 480 mL feeding pump. After n-BuLi was added, the reaction mixture was stirred for 12 hours while slowly raising the temperature of the reactor. After 12 hours of reaction, an equivalent of methyl (6-t-butoxy hexyl) dichlorosilane (326 g, 350 mL) was quickly added to the reactor. After stirring for 12 hours while slowly raising the reactor temperature to room temperature, the reactor temperature was cooled to 0 r again, and then 2 equivalents of t-BuN¾ was added thereto. Stirring for 12 hours while slowly raising the reactor temperature to room temperature. After 12 hours of reaction, THF was removed and 4 L of nucleic acid was added to obtain a filter solution from which salt was removed through labdori. After adding the filter solution to the reactor again, the nucleic acid was removed at 70 ^° C to obtain a yellow solution. Obtain the yellow solution through 1H-NMR through methyl (6-t-butoxynuclear) (tetramethyl CpH) t-butylaminosilane (Methyl (6-t-but hoxyhexy 1) (tetramethylCpH) t- Butylaminosi lane) compound was confirmed. n-BuLi and ligand dimethyl (tetramethyl CpH) t-butylaminesilane

TiCl ₃ (THF) ₃ (10 mmol) was quickly added to the dilithium salt of a -78 ^° C ligand synthesized in THF solution from (Dimethyl (tetramethylCpH) t-Butylaminosi lane). The reaction solution was stirred for 12 hours while slowly raising the temperature to _78 ^° C. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution was obtained. After removing THF from the reaction solution, nucleic acid was added to filter the product. After removing the nucleic acid from the resulting filter solution, desired t-butoxynucleosilmethylsilyl (Nt-butylamido) (2, 3, 4, 5-tetramethylcyclopentadienyl) -titanium dichloride (t) from 1H-NMR -butoxyhexylme仕iylsilyl (Nt-bu仕lylamidoX SAS- te竹ame仕iylcyclopentadienyl) -titaniumdichloride, [methyl (6-t-buthoxyhexyl) silyl (ri5- tetrame仕iylCp) (t-Butylamido)] TiCl 2) of (tBu It was confirmed that -0- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ (CH ₃ ) ₄ ) (tBu-N) TiCl ₂ .

1 H-NMR (CDCls): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 抑), 1.8 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), 0.7 ( s, 3H) <Production Example of Hybrid Supported Metallocene Catalyst>

 Example 1 Hybrid Supported Metallocene Catalyst

 (1) Carrier Preparation

Silica (SP 952, manufactured by Grace Davision) was dehydrated and dried under vacuum at a temperature of 600 ^° C. for 12 hours.

(2) Preparation of Mixed Supported Metallocene Catalysts

Toluene solution, about 3.0 kg was added to a 20 L stainless steel high pressure reactor, and about 1000 g of the silica carrier prepared in step (1) was added thereto, followed by stirring while raising the reactor temperature to about 40 ^° C. After sufficiently dispersing the silica for about 60 minutes, about 1st metallocene compound prepared in Synthesis Example 1 2019/156482 1 »（： 1 ^ 1 {2019/001535

After dissolving 0.1 ₁ ^ 1 in a solution state, the mixture was stirred for about 2 hours, the stirring was stopped, and the reaction solution was left to stand for about 30 minutes. Then, the reaction solution was decanted (< ₀₃₁ 1 ₀₁₁ ). Subsequently, the reactor was charged with 10 '8% methylaluminoxane (■ ()) / toluene solution 5.4.

Stirred. Thereafter, the stirring was stopped presentation (line size)]) dikaen the reaction solution after about 30 minutes and was allowed to stand for you比_§).

After stirring for about 2 minutes, about 0.1 mi of the second metallocene compound prepared in Synthesis Example 2 was dissolved in a solution state, and reacted with stirring for about 2 hours. After that, stop the stirring and settle for about 30 minutes.

The slurry was transferred to a filter drier (^ 11 a) and the nucleic acid solution was filtered off. Drying under reduced pressure at about 50 kPa for about 4 hours yielded a hybrid supported metallocene catalyst. Example 2 Hybrid Supported Metallocene Catalyst

A hybrid supported metallocene catalyst was produced in the same manner as in Example 1, except that the temperature to be introduced was raised to 130 I: instead of 110 I :. Example 3 Hybrid Supported Metallocene Catalyst

When adding 10% methylaluminoxane (^ 0) / toluene solution in Example 2

Except, a hybrid supported metallocene catalyst was prepared in the same manner as in Example 2. 2019/156482 1 »（： 1 ^ 1 {2019/001535

Comparative Example 1 Hybrid Supported Metallocene Catalyst

 (1) Carrier Preparation

 Silica 952, (manufactured by High 0 ^^ 011), was dehydrated and dried under vacuum at a temperature of 600 V for 12 hours.

(2) Preparation of mixed supported metallocene catalyst

Into a stainless steel (20) into a high pressure reactor in about 3.0 1 _¾ toluene solution, about 1000 yaw of the silica carrier prepared in step (1) was added, and stirred while raising the reactor temperature to about 40 (:). After sufficiently dispersing the silica for about 60 minutes, about 0.1 ₁ ^ () 1 of the _first metallocene compound prepared in Synthesis Example 1 was dissolved in a solution state, added thereto, and stirred for about 2 hours.

The reaction solution was decanted ⁰ (1 _{6 € 31} 1 ₀₁₁ ). Thereafter, 10% methylaluminoxane () / toluene solution was added to the reactor in 7.4.

Stirred. Then, the reactor temperature was lowered again to 40 X, the stirring was stopped, allowed to stand for about 30 minutes ( ₃₆ 1 比_§ ), and then the reaction solution was added.

After stirring for about a minute, about 0.1 mi of the second metallocene compound prepared in Synthesis Example 2 was dissolved in a solution state, and reacted with stirring for about 2 hours. After that, stop the stirring and settle for about 30 minutes.

The slurry was transferred to a filter drier (11 la) and the nucleic acid solution was filtered off. Drying under reduced pressure at about 50 kPa for about 4 hours yielded a hybrid supported metallocene catalyst. 2019/156482 1 »（： 1 ^ 1 {2019/001535

Comparative Example 2: Hybrid Supported Metallocene Catalyst

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 1, except that the temperature to be charged was lowered to 110 I: rather than 60 I :. Comparative Example 3 Hybrid Supported Metallocene Catalyst

In the same manner, a hybrid supported metallocene catalyst was prepared. Comparative Example 4 Hybrid Supported Metallocene Catalyst

A hybrid supported metallocene catalyst was prepared in the same manner as in Comparative Example 1, except that the temperature to be charged was 60 ° C .:

 (1) carrier preparation

Silica 952, ⁽ manufactured ^by 0 ^^ ₀₁₁ ), was dehydrated and dried under vacuum at room temperature for 12 hours.

(2) Preparation of Mixed Supported Metallocene Catalysts

20 stainless steels (toluene solution about 3.0 1 _¾ in a high-pressure reactor, about 1000 sugars of the silica carrier prepared in step (1) was added,

After raising, the mixture was stirred for about 12 hours with about 200 agents. Then lower the reactor temperature to 40 I: and stop the agitation for about 30 minutes

2019/156482 1 »（： 1 ^ 1 {2019/001535

After stirring for about 1 minute, about 0.1 11101 of the first metallocene compound prepared in Synthesis Example 1 was dissolved in a solution state, added, and stirred for about 2 hours to react. Thereafter, about 0.11 111 () 1 of the second metallocene compound prepared in Synthesis Example 2 was dissolved in a solution state, followed by stirring for about 2 hours. After that, the stirring was stopped and allowed to stand for about 30 minutes (36 1 11 塔), and then the reaction solution was

Inject about 3.0 urine nucleic acid into the reactor, transfer the nucleic acid slurry to the filter drier (A), filter the nucleic acid solution

 A supported metallocene catalyst was prepared. Comparative Example 6: Hybrid Supported Metallocene Catalyst

 (1) Carrier Preparation

Silica 952, （¾ 6

Manufacturing)

Dehydration and drying were performed under vacuum at temperature for 12 hours.

(2) Preparation of mixed supported metallocene catalyst

20 stainless steels (about 3.0 1 _¾ of toluene solution was added to a high-pressure reactor, and about 1,000 sugars of the silica carrier prepared in step (1) were added thereto, followed by stirring while raising the reactor temperature to about 40 ×. ^' After sufficient dispersion of silica for about 60 minutes,

After uploading, it was stirred for about 12 hours at about 200 印₁₁₁ . Then, the reactor temperature was lowered to 40 X: and 10 ¾ _> methylaluminoxane (■ （)) / toluene solution was removed.

2019/156482 1 »（： 1 ^ 1 {2019/001535

Toluene about 3.0 in the reaction solution thus recovered

After the solution was added and stirred for about 10 minutes, about 0.1 _{> 110} 1 of the first metallocene compound prepared in Synthesis Example 1 was dissolved in a solution state, and the mixture was stirred and reacted for about 2 hours. Thereafter, about 0.1 ₁ ^ of the second metallocene compound prepared in Synthesis Example 2 was dissolved in a solution state, followed by stirring for about 2 hours. After this, stirring was stopped and allowed to stand for about 30 minutes (for comparison), and then the reaction solution was decanted. About 3.0 nucleic acids were introduced into the reactor and the nucleic acid slurry was transferred to a filter drier (Lara) and the nucleic acid solution was filtered off. The mixture was dried under reduced pressure for about 4 hours at about 50 to prepare a hybrid supported metallocene catalyst. In the process of preparing the hybrid supported catalyst according to Examples 1 to 3 and Comparative Examples 1 to 6, the first metallocene was prepared. The supported content and supported temperature of the compound and the second metallocene compound and the promoter are shown in Table 1 below.

Table 1

2019/156482 1 »（： 1 ^ 1 {2019/001535

In the preparation of the supported catalyst in Table 1, the first metallocene compound (precursor 1), the second metallocene compound (precursor 2), and the co-catalyst (show 0) were classified according to the order of '' 广.

<Polymerization Example of Olefin Monomer>

 Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 6: Homopolymerization of ethylene

Under the conditions as shown in Table 2, the ethylene homopolymerization reactions of Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 6 were carried out using the hybrid supported metallocene catalysts of Examples 1 to 3 and Comparative Examples 1 to 6 Was performed. First, add 2 triethylaluminum (1 £ show 2 mL （1 M 111 1¾, to 2 high pressure reactors, show 1 加 句 high pressure reactor, add 0.6 ¾ nucleic acid), and stir at 500 The temperature was raised to 80 X :. The hybrid supported catalyst and the nucleic acid were added to the reactor, followed by addition of 0.2 no silver of the nucleic acid. When the internal temperature of the reactor reached 80 I :, the mixture was reacted for 1 hour with stirring at 500 111 under ethylene pressure 30. Obtained after completion of reaction

Dried. In the polymerization process of Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 6, the activity of the catalyst and the physical properties of the prepared polyolefin were measured as follows. The results are shown in Table 2 below.

(1) Catalytic activity (Activity, kgPE / gSi0 ₂ ): The weight of the catalyst used in the polymerization reaction of Preparation Example and Comparative Preparation Example and the weight of the polymer produced from the polymerization reaction were measured to determine the polymerization reaction of Preparation Example and Comparative Preparation Example. The catalytic activity (act ivi ty) of each of the examples and comparative catalysts used was calculated. Specifically, as described above, the weight (kg) of the polyethylene obtained after the polymerization process and the drying process is measured to be a kgPE value, and the weight (g) of the supported catalyst used in the polymerization process is gSi <¾, thus obtained. The weight (kg) of polyethylene was measured and the value obtained by dividing the kgPE value by the weight (g) _g Si0 ₂ of the supported catalyst was shown as catalyst activity.

(2) Weight average molecular weight (Mw) and molecular weight distribution (MTO, polydi spers i ty index): gel permeation chromatography (GPC, gel permeat ion chromatography,

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of polyethylene were measured using the product made by Water Corporation), and the molecular weight distribution (MffD, Mw / Mn) was calculated by dividing the weight average molecular weight by the number average molecular weight. Specifically, Water Permeation Chromatography (GPC) apparatus was used Waters PL-GPC220 instrument, Polymer Laborator ies PLgel MIX-B 300 _ length column was used. At this time, the measurement temperature was 160 ° C, 1,2,4-trichlorobenzene (1,2,4-Tr i chlorobenzene) was used as a solvent, the flow rate was 1 mL / min. Polyethylene samples according to Preparation Examples and Comparative Preparation Examples contained trichlorobenzene (1,2,4-B 0.0125%) using a GPC analysis device (PL-GP220), respectively.

Tr ichlorobenzene) was dissolved in 160 ° C for 10 hours, pretreated, prepared at a concentration of 10 mg / 10mL, and then supplied in an amount of 200 y L. The calibration curves formed using polystyrene standard specimens were used to derive the values of Mw and Mn. The weight average molecular weight of the polystyrene standard specimens is 2000 g / mol, 10000 g / mol, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 9 types of dragon / _{11101, 4000000} dragon / ₁₁₁₀₁ , 10000000 dragon / MUI were used.

(3) Particle size distribution analysis (PSD): The polymers were separated by particle size using sieve (sieve, size 850 pm, 500 pm, 300 jm, 180 _jM n). Specifically, using the sieve as described above, respectively, the particle size of the polymer is more than 850, 0850), more than 500 _ 850, or less (> 500), more than 300 _{^ ■} less than 500 m if (ñ300), 180 _/ if 300 m or less in excess of Fe (> 300), that, based on the, total weight of the total polymer hanhue measuring the weight of the polymer corresponding to the differential case state (Fine) of less than 180 pm particle The weight of polymer separated by size is expressed as percentage (wt%). The results of particle size distribution (PSD) analysis are based on the weight values separated by sieve in the laboratory, without using a specific device or based on specific criteria.

Shown as PSD.

(4) Apparent Density (BD): Measured according to the method of ASTM D 1895 Method A. Specifically, after filling a 100 mL volume of SUS container with polymer, the polymer weight (g) at this time was measured and measured per unit volume. Expressed in weight (g / mL).

(5) A1 loading rate (%) measurement: The A1 loading rate in the supported catalyst was measured by an Inductively Coupled Plasma Spectrometer (ICP) analysis method. At this time, the A1 loading rate (%) represents the amount of the actually supported promoter relative to the amount of promoter (A1) put in the preparation of the supported catalyst as a percentage value. Specifically, the equipment used for analysis was ICP-OES (Perkin Elmer) and the analysis conditions were set to Plasma Gas 12 L / min, Auxiliary Gas 0.2 L / min, Nebulizer Gas 0.8 L / min, and RF Power was 1300 WATTS, Sample flow rate was measured by Radial View at 1.50 mL / min. Table 2

We can see that from the results of Table 2, Production Examples 1 to 3 is able to prepare a polyethylene that meets both the 0.40 / 0.41 to _{§ /!}此broad molecular weight distribution of a high bulk density and 4.2 to 4.3 for. In particular, Preparation Examples 1 to 3 had a catalytic activity of 9.9

To 12 1 녠 ¾ / _§ 0 ₂ while maintaining a high particle size and narrow distribution, the apparent density has the advantage of rising. The resulting polymer particles are dense 2019/156482 1 »（： 1 ^ 1 {2019/001535

It can be seen that it can be produced and can increase productivity by improving the settling efficiency when applied to actual pilot process or continuous process. The hybrid supported catalysts of Examples 1 to 3 used in the polyethylene polymerization process of Preparation Examples 1 to 3 can broaden the polymer! ■!) By supporting the first metallocene precursor before the supported catalyst. The processability of the polymer can be improved. In addition, the hybrid supported catalyst of Example 1 can support the splitting of the promoter sequentially at a high temperature to evenly support the promoter to the inside of the carrier, thereby significantly increasing the apparent density of the resulting polymer. In particular, when the contents of the supported catalyst in the catalysts were analyzed as 10 ³ with respect to the hybrid supported catalysts of Examples 1 to 3, although the same amount of the promoters were added to Comparative Examples 1 to 6, the promoters were maintained at high temperature. It can be seen that the loading ratios of Example 1 to 3 which were dividedly supported were 89% and 90%. On the other hand, Comparative Production Examples 1 to 6 could not obtain a polymer that satisfies the apparent density and molecular weight distribution 1)) and the particle size distribution at the same time.

The apparent density of polyethylene was lower than that of Preparation Examples 1 to 3 by applying the catalysts of Comparative Examples 1 to 3 all at once or partly supported at a low temperature of 80. In Comparative Production Example 4, even when the promoter was supported at a high temperature of 110 X :, even when the hybrid supported catalyst of Comparative Example 4, which was supported at one time without split injection, was used, the apparent density of polyethylene was lower than that of the split injection. It can be seen that. In particular, in Comparative Examples 1 to 4, the first metallocene compound was supported prior to the support of the promoter, so that the molecular weight distribution of the polymer (which could be widely secured, but the particle size distribution of the polymer was wide and the apparent density 犯 £ ₁ ) was low. It is difficult to expect productivity gains. In Comparative Production Examples 5 and 6, the catalyst was first supported and the catalyst By applying the hybrid supported catalyst carrying the precursor, the molecular weight distribution (MWD) of the polymer dropped and appeared narrow. Preparation Example 4 and Comparative Preparation Examples 7 to 9: Ethylene-1-nucleene copolymerization

Under the conditions as shown in Table 3 below, the ethylene- 1 -nuxene copolymerization reaction of Preparation Example 4 and Comparative Preparation Examples 7 to 9 was carried out using the hybrid supported metallocene catalyst of Example 1 and Comparative Examples 1, 4 and 5. Was performed. At this time, the polymerization reactor was a continuous polymerization reactor, that is, a loop slurry reactor, which is an isobutane Slurry loop process, the reactor volume was 140 L, and the reaction flow rate was operated at about 7 m / s. Gases (ethylene, hydrogen) and comonomer 1-hexene required for polymerization are continuously and continuously injected, and the individual flow rate is adjusted to the target product. The concentration of all gases and comonomers 1-hexene was confirmed by on-line gas chromatograph. Supporting monomers were introduced into isobutane slurry, reactor pressure was maintained at about 40 bar, and polymerization temperature was performed at about 93 ^° C. It was. Table 3 shows the results of evaluating the activity of the catalyst and the physical properties of the prepared polyolefin in the polymerization process of Preparation Example 4 and Comparative Preparation Examples 7 to 9. Among these, catalyst activity and Mw, MWD, BD were measured by the method as mentioned above.

(6) Ethylene load (C2) Weight (kg / h): Ethylene consumption per hour (polymer production amount), ie ethylene per unit time, when the ethylene- 1-nuxene copolymerization reaction is carried out under the polymerization conditions as described above. Load shedding weight (kg / h) was measured.

(7) MI _{2. i6} and MFRR (21.6 / 2.16): Melt Index (MI _2.16, Melt Index) was measured according to ASTM D 1238 (Condition E, 190 ^° C, 2.16 kg load). On the other hand, the melt flow index 七 1 _{0 ¥} yaw root ratio 比 ，! ¾ ， 21.6 / 2.16) MFR _21.6 was calculated by dividing by MFR _2.16 , MFR _21.6 measured under a temperature of 190 ^° C and a load of 21.6 kg according to ISO 1133, MFR _2.16 measured under a temperature of 190 ^° C and a load of 2.16 kg according to ISO 1133 It was. (8) Density: Measured according to the method of ASTM D 1505.

(9) Slurry density (DI, slurry density): Slurry density was measured using radiation as a value representing the amount of polymer per unit volume in a slurry loop reactor.

(10) Settling efficiency (SE,%): The settling efficiency was measured as defined by the following formula (1).

 [Calculation formula 1]

 Settling efficiency (%) = amount of ethylene used / (ethylene used + solvent content) 父 100

Table 3

From the results of Table 3, Preparation Example 4 is a high apparent by using the hybrid supported catalyst of Example 1 to carry the first metallocene precursor first, and then to carry a split catalyst and to support the second metallocene precursor It can be seen that it is possible to effectively produce polyolefins having a density and a wide molecular weight distribution. Particularly, in Preparation Example 4, after the primary catalyst was first supported at a high temperature of 110 ° C, the residue was sequentially supported at 40 ^° C, and then dividedly supported so as to evenly support the promoter to the inside of the carrier. Continuous polymerization under the density (slurry densi ty, DI) significantly increased the settling efficiency (SE) and ethylene rod while having high activity. Specifically, the settling efficiency of (Example 4) was further improved by about 7.9% to about 11.5% compared to Comparative Preparation Examples 7 to 9. Thus, the ethylene load weight per hour of Preparation Example 4 was compared. Compared to Preparation Examples 7 to 9 further increased by about 17.6% to about 25%, it can be seen that the productivity in the slurry loop polymerization process, which is a pilot continuous process, can be significantly improved.

Claims

2019/156482 1 »（： 1 ^ 1 {2019/001535 【claims】 【claim 1】 A step of supporting at least one first metallocene compound on a silica carrier; Contacting the silica carrier on which the first metallocene compound is supported with at least one aluminum-based promoter compound to support the aluminum-based promoter compound on the silica carrier; and the silica on which the aluminum-based promoter compound is supported. Supporting at least one second metallocene compound on the carrier; The aluminum-based cocatalyst compound includes 50 wt% to 90 wt% of the total amount of the first dose at 100 X: to 150 ° C, and the remainder of the total dose is -5 X to 40 X: A method for producing a hybrid supported metallocene catalyst, which is supported on a silica carrier by a secondary injection method at a secondary temperature. [Claim 2] The supporting amount of the first metallocene compound and the second metallocene compound is subtracted from 0.01 1 based on the amount of the silica carrier, respectively. Manufacturing method. [Claim 3] The method of claim 1, wherein the first metallocene compound and the second metallocene compound are each represented by any one of the following Chemical Formulas 1 to 5.

[Formula 1]

In Chemical Formula 1, 2019/156482 1 »（： 1 ^ 1 {2019/001535

Any one selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, 7-tetrahydro-1 -indenyl, and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms;

And 0 are the same as or different from each other, and each independently hydrogen, alkyl of 01 to 020, alkoxy of 310 to 310, alkoxyalkyl of C1 to 020, aryl of 06 to 020, aryloxy of 06 to 010, 02 to 020 Alkenyl, 07-07

Not;

 Each independently represents a halogen atom, alkyl of 01 to 020, alkenyl of 02 to (10: 10, alkylaryl of 07 to 040, arylalkyl of 01 to 040, aryl of 06 to 020, substituted or unsubstituted 01 to Alkylidene of 020, substituted or unsubstituted amino group, alkylalkoxy of 02-020, or arylalkoxy of 07-040;

 II is 1 or 0;

Any one selected from the group consisting of cyclopentadienyl, indenyl, 4, 5,6, 7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms;

To 020 alkyl, 01 to <310 alkoxy, 02 to 020 alkoxyalkyl, 06 to 020 aryl, 06 to （: 10 aryloxy, 02 to 020 alkenyl, (21 to 2019/156482 1 »（： 1 ^ 1 {2019/001535

040 alkylaryl, 07-040 arylalkyl, 08-040 arylalkenyl, or 02-010 alkynyl;

 Each independently represents a halogen atom, alkyl of 01-020, alkenyl of 02-(: 10), alkylaryl of 07-040, arylalkyl of 07-040, aryl of 06-020, substituted or unsubstituted 01-020 Alkylidene of, substituted or unsubstituted amino group, alkylalkoxy of 02-020, or arylalkoxy of 07-040;

Tomb ¹ is。 ³ !? With rings

Crosslink the ring, or

At least one or a combination of radicals comprising carbon, germanium, silicon, phosphorus or nitrogen atoms which crosslink the ring to ² ;

 111 is 1 or 0;

[Formula 3]

 Metal;

Tadienyl, indenyl, 4, 5,6, 7-tetrahydro-1-indenyl and fluorenyl radicals, which can be substituted with hydrocarbons having 1 to 20 carbon atoms;

 Is hydrogen, 01-020 alkyl, 01- (310 alkoxy, 02-020 alkoxyalkyl, 06-020 aryl, 06- (aryloxy of 0, 02-

020 alkenyl, 07 to 040 alkylaryl, (3- to 040 arylalkyl, 08 to

040 arylalkenyl or 02-010 alkynyl;

 Each independently represents a halogen atom, alkyl of 01 to 020, and 02 to

10 alkenyl, 07 to 040 alkylaryl, 0 to 1 to 040 arylalkyl, 06 to

020 aryl, substituted or unsubstituted 01-020 alkylidene, substituted or unsubstituted amino group, 0.2-020 alkylalkoxy, or 07-040 arylalkoxy;

： 6 ² is

Carbon, germanium, silicon, phosphorus which crosslinks the ring and 1 2019/156482 1 »（： 1 ^ 1 {2019/001535

Or one or more or a combination of radicals containing nitrogen atoms;

Each of which is independently selected from the group consisting of urine, wherein is independently (alkyl of 1 to 020, alkyl substituted, aryl substituted or substituted aryl,

[Formula 4]

In Chemical Formula 4,

Mod ¹ to ^ and

To ^{4 '} are the same as or different from each other, and each independently hydrogen, an alkyl group of 01 to 020, an alkenyl group of 02 to 020, an aryl group of 06 to 020, an alkylaryl group of 07 to 020, and an arylalkyl group of 07 to 020 Or an amine group of 01 to 020, and two or more adjacent ones of the II ¹ to II ⁴ and the parent ^{1 '} to II ^4' may be connected to each other to form one or more aliphatic rings, aromatic rings, or heterocycles. ;

 And minutes are the same or different from each other, and each independently hydrogen, an alkyl group of 01 to 020, a cycloalkyl group of 03 to 020, an (alkoxy group of 1 to 020, an aryl group of 06 to 020, an aryloxy group of 06 to 010) , An alkenyl group of 01 to 020, an alkylaryl group of 07 to 040, or an arylalkyl group of 07 to 040;

 # Is 02-020 alkylene group, 03-020 cycloalkylene group, 06-020 aryltene group, 07-040 alkylarylene group, or 07-040 arylalkyltene group;

 4 is a Group 4 transition metal;

VII and 2: ⁵ are the same as or different from each other, and each independently a halogen, an alkyl group of 01 to 020, an alkenyl group of 02 to 020, an aryl group of 06 to 020, 2019/156482 1 »（： 1 ^ 1 {2019/001535

Nitro groups, amido groups, (1 to 020 alkylsilyl groups, (1 to 020 alkoxy groups, 02 to 020 ester groups, or 01 to 020 sulfonate groups);

[Formula 5]

In Chemical Formula 5,

II ⁵ and ^' are each independently hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, silyl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, 7 to 7 carbon atoms A metalloid of a Group 4 metal substituted with 20 arylalkyl or hydrocarbyl; The II ⁵ and the parent ^{5 ′} or two II ^{5 ′} may be linked to an alkylidine comprising alkyl having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms to form a ring;

^ Is independently hydrogen, halogen atom, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms, 1 Alkoxy of 20 to 20, aryloxy or amido of 6 to 20 carbon atoms; The two or more yaw II ⁶ out of ⁶ are connected to each other and can form an aliphatic ring or an aromatic ring;

 A substituted or unsubstituted aliphatic or aromatic ring, and the substituents substituted in the above are halogen atoms, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, Arylalkyl having 7 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, and amido; when the substituents are plural, two or more substituents from the substituents may be linked to each other to form an aliphatic or aromatic ring. Can form;

M ⁵ is a Group 4 transition metal; 2019/156482 1 »（： 1 ^ 1 {2019/001535 3 and minute are each independently halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, of 7 to 20 carbon atoms Alkylaryl, arylalkyl having 7 to 20 carbon atoms, alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms or alkylidene having 1 to 20 carbon atoms.

[Claim 4]

 The method of claim 3,

 The metallocene compound represented by Chemical Formula 1 is one of the following structural formulas,

 Process for preparing hybrid supported metallocene catalyst:

2019/156482 1 »（： 1/10 公 019/001535

[Claim 5]

 The method of claim 3,

 The metallocene compound represented by Formula 2 is one of the following structural formulas,

 Method for producing a hybrid haze metallocene catalyst.

2019/156482 1 »（： 1/10 公 019/001535

[Claim 6]

 The method of claim 3,

 The metallocene compound represented by Formula 3 is one of the following structural formulas,

 Method for producing a hybrid supported metallocene catalyst.

2019/156482 1 »（： 1/10 公 019/001535

:

[Claim 7]

 The method of claim 3,

 The metallocene compound represented by Formula 4 is one of the following structural formulas,

 Method for producing a hybrid supported metallocene catalyst.

[Claim 8]

The method of claim 3, 2019/156482 1 »（： 1/10 公 019/001535

The metallocene compound represented by Formula 5 is one of the following structural formulas,

 Method for producing a hybrid supported metallocene catalyst.

In the above formula, each II ⁷ is independently hydrogen or methyl; 5 ⁵ and silver are each independently methyl _, dimethylamido or chloride _.

[Claim 9]

 The method of claim 1,

The aluminum-based promoter compound is 60 to 90% by weight of the total amount

Supported on silica carrier,

Method for producing hybrid supported metallocene catalyst. 2019/156482 1 »（： 1 ^ 1 {2019/001535

[Claim 10]

 The method of claim 1,

 The aluminum-based catalyst compound is represented by the following formula (6), a method for producing a hybrid supported metallocene catalyst:

Halogen, a hydrocarbyl group of 01 to 020, or a hydrocarbyl group of € 1 to 020 substituted with halogen;

 1 is 0 or 1;

 X is an integer of 2 or more.

[Claim 11]

 The method according to claim 11 or 10,

 The aluminum-based promoter compound may be an alkylaluminoxane compound selected from the group consisting of methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane; Or trialkylaluminum selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trinuclear silaluminum, trioctylaluminum and isoprenylaluminum,

 Method for producing hybrid supported metallocene catalyst.

[Claim 12]

 The method of claim 1,

The supported amount of the aluminum-based promoter compound is 5 _ ₀₁ / solvent to 15 ■ ₀₁ / yong, based on the silica carrier 1

Method for producing a hybrid supported metallocene catalyst. 2019/156482 1 »（： 1 ^ 1 {2019/001535

[Claim 13]

According to claim _1,

 The silica carrier is one or more selected from the group consisting of silica, silica-alumina, and silica magnesia,

 Method for producing hybrid supported metallocene catalyst.

[Claim 14]

 The method of claim 1,

 Mainly comprising the step of supporting at least one borate-based co-solvent compound on the aluminum carrier-supported silica carrier,

 Method for producing a hybrid supported metallocene catalyst.

[Claim 15]

 The method of claim 1,

 The borate cocatalyst compound is a borate compound in the form of a trisubstituted ammonium salt, a borate compound in the form of a dialkyl ammonium salt, or a borate compound in the form of a trisubstituted phosphonium salt,

 Method for producing a hybrid supported metallocene catalyst.

[Claim 16]

 A process for producing a polyolefin, comprising polymerizing an olefinic monomer in the presence of a hybrid supported metallocene catalyst prepared according to any one of claims 1 to 15.

[Claim 17]

 The method of claim 16,

The apparent density of polyolefin is 0.38

More than, molecular weight distribution (¾ 細 /) is 3.5 or more ，

Method for producing polyolefin. 2019/156482 1 »（： 1 ^ 1 {2019/001535

[Claim 18]

 The method of claim 16,

 A settling efficiency of 65% to 80%, defined by Formula 1 below, a method for producing a polyolefin.

 [Calculation 1]

 Settling efficiency） = Ethylene Consumption 八 Ethylene Consumption + Solvent Content）

100