WO2020174346A1 - NOVEL TETRAARYLBORATE COMPOUND, CATALYST COMPOSITION COMPRISING SAME, AND METHOD FOR PREPARING ETHYLENE HOMOPOLYMERS OR COPOLYMERS OF ETHYLENE AND α-OLEFIN BY USING SAME - Google Patents

Abstract

The present invention relates to a novel tetraarylborate compound, a catalyst composition comprising same, and a method for preparing ethylene homopolymers or copolymers of ethylene and α-olefins by using same. In detail, the tetraarylborate compound has the excellent thermal stability and can be completely dissolved in an aliphatic hydrocarbon-based solvent, thereby facilitating operation of commercial processes and effectively inducing activation of a single-site catalyst. When used as a catalyst activator, the tetraarylborate compound allows high catalytic activity and can provide high molecular weight ethylene homopolymers and ethylene-based copolymers selected from copolymers of ethylene and α-olefin, and the like.

Description

2020/174346 1 ?€1/162020/051519

Specification

Name of the invention: a novel tetraaryl borate compound, a catalyst composition comprising the same, and an ethylene homopolymer or ethylene using the same

«- Manufacturing method of olefin copolymer

Technical field

[1] The present invention relates to a tetraaryl borate compound, a catalyst composition comprising the same, and a method for producing an ethylene homopolymer or a copolymer of ethylene and (X-olefin) using the same.

Background

[2] Conventionally, in the production of homopolymers of ethylene or copolymers with X-olefins,

In general, the main catalyst component of titanium or vanadium compounds and alkyl aluminum

The so-called Ziegler-Natta catalyst system, which is composed of the co-catalyst component of the compound, has been used. By the way, the Zeigler-Natta catalyst system exhibits high activity against ethylene polymerization, but due to the non-uniform catalytic activity point, the molecular weight distribution of the resulting polymer is generally wide. In particular, in the copolymer of ethylene and (X-olefin, there was a disadvantage that the crude composition was not uniform.

[3] Metallocene of transition metals in Group 4 of the periodic table, such as titanium, zirconium, and hafnium recently

The so-called metallocene catalyst system was developed, consisting of a compound and a co-catalyst, methylaluminoxane (1st high school 61; 11)^11111111100116). Because the metallocene catalyst system is a homogeneous catalyst having a single catalytic activity point, the existing Ziegler- Compared to the Natta catalyst system, the molecular weight distribution is narrow and it has the characteristics of being able to produce polyethylene having a uniform composition. For example, in Patent Documents 1 to 1, ethylene is highly active by activating a metallocene compound with the co-catalyst methylaluminoxane. It was announced that polyethylene having a molecular weight distribution (Mw/Mn) in the range of 1.5 to 2.0 can be produced by polymerization. However, it is difficult to obtain a polymer having a high molecular weight with the catalyst system. In particular, when applied to a solution polymerization method conducted at a high temperature of 100 °0 or higher, the polymerization activity rapidly decreases and |3 -hydrogen depletion reaction is predominant, so the weight average molecular weight It is known that (Mw) is not suitable for producing high molecular weight polymers of 100,000 or more.

[4] On the other hand, ethylene alone polymerization or ethylene and (X-olefin

As a catalyst system capable of producing polymers with high catalytic activity and high molecular weight in copolymerization, a so-called geometrically constrained non-metallocene catalyst (also known as a single active point catalyst) in which transition metals are connected in a ring shape has been disclosed. An example of linking an amide group to one cyclopentadiene ligand in a cyclic form is presented, and Patent Document 13 shows an example of a catalyst in which a phenolic ligand as an electron donor compound is linked to a cyclopentadiene ligand in a cyclic form. In the case of catalysts, due to the lowered stereoscopic effect of the catalyst itself, 2020/174346 2 ?€1/162020/051519

Although the reactivity has been remarkably improved, research on a catalyst that provides excellent activity and excellent copolymerization properties at high temperatures commercially and a method for activating the catalyst is becoming important.

[5] In addition, as part of a study on a catalyst system capable of producing a polymer having high catalytic activity and high molecular weight in ethylene alone polymerization or copolymerization of ethylene and (X-olefin, etc.) under solution polymerization conditions, Patent Documents 14 to 17 Alternatively, a catalyst system including a cocatalyst provided in the form of a slurry is disclosed. The cocatalyst disclosed in these is supplied to the reactor as a cocatalyst solution including a toluene solution, etc., and is continuously or discontinuous with the metallocene compound. In the case of employing a catalyst system provided in a solid state, the supply device such as a pump used in a production process carried out at a mass scale may be disturbed, preventing stable operation. In addition, due to the solubility problem of the catalyst system Since an aromatic hydrocarbon-based solvent such as toluene must be used, problems such as residual ethylene alone polymerization or a copolymer of ethylene and (X-olefin, etc.), which are the final products, cause odor, and additional processes are involved to remove them. Under the background of such research, research to solve the problems of the above-described catalyst system and to provide a catalyst system capable of producing a high catalytic activity and high molecular weight polymer in ethylene alone polymerization or copolymerization with ethylene and olefins under solution polymerization conditions is continuing. Is being demanded.

[6] (Patent Document 1) European Patent Publication No. 320, 762 (1989.06.21)

[7] (Patent Document 2) European Patent Publication No. 372, 632 (1990.06.13)

[8] (Patent Document 3) Japanese Patent Application No. 63-092621 (1988.04.23)

[9] (Patent Document 4) Japanese Patent Laid-Open No. 02-84405 (1990.03.26)

[1] (Patent Document 5) Unexamined Patent Publication No. 03-2347 (1991.01.08)

[11] (Patent Document 6) European Patent No. 0416815 (1991.03.13)

[12] (Patent Document 7) European Patent No. 0420436 (1991.04.03)

[13] (Patent Document 8) European Patent No. 0842939 (1998.05.20)

[14] (Patent Document 9) \¥0 98/06728 (1998.02.19)

[15] (Patent Document 10) O 01/42315 (2001.06.14)

[16] (Patent Document 11) European patent system (Shoo 16715 No. (1997.08.13)

[17] (Patent Document 12) European Patent No. 0420436 (1996.08.14)

[18] (Patent Document 13) European Patent No. 08 Show 939 (1998.05.20)

[19] (Patent Document 14) European Patent No. 0889062 (1999.01.07)

[2 (Patent Document 15) European Patent No. 088 ⁷ 355 (1998.12.30)

[21] (Patent Document 16) US Patent No. 6613850 (2003.09.02)

[22] (Patent Document 1, US Patent No. 6660816 (2001.07.19)

Detailed description of the invention 2020/174346 3 1^(:1^2020/051519

Technical task

[23] In order to overcome the problems of the prior art, the present inventors conducted extensive research, and as a result of using a tetraarylborate compound containing a cation having an alkylidene anilinium structure as a co-solvent, the solubility of an aliphatic hydrocarbon-based solvent was determined. The present invention was completed by discovering that it can effectively improve the activity of a single active point catalyst.

[24] One object of the present invention is to provide a new tetraarylborate compound useful as a cocatalyst for the production of an ethylene homopolymer or a copolymer of ethylene and (X-olefin), and to provide a catalyst composition containing this and a single active point catalyst. There is.

[25] One object of the present invention is to provide a method for economically producing an ethylene homopolymer or a copolymer of ethylene and (X-olefin) from a commercial point of view by using the above catalyst composition.

Problem solving means

[26] In order to achieve the above object, in the present invention,

Tetraarylborate compounds are provided.

3 30) cycloalkyl, ((：1 30) alkyl 6 30) aryl, (6 30) aryl,

(06 30) Aryloxy, ((：1 30) Alkyl (06 30) Aryloxy, (06 30) Aryl(0 30) Alkyl and ((0-030) Alkyl 6 30) Aryl) ((1 30) It may be further substituted with one or more substituents selected from alkyl, etc.] In addition, in the present invention,

Tetraarylborate compounds; An ethylene homopolymer or a transition metal catalyst composition for producing a copolymer of ethylene and (X-olefin) containing a single active point catalyst containing a group 4 transition metal; and an aluminum compound is provided.

[35] In the present invention, the ethylene homopolymer or ethylene and (X-olefin

Ethylene homopolymer using a transition metal group composition for preparing a copolymer or 2020/174346 4 ?€1/162020/051519

A method for preparing a copolymer of ethylene and (X-olefin is provided).

[36] In the present invention, the tetraaryl borate compound of Formula 1 and the

Injecting a catalytically activated preparation containing the organic solvent used in the preparation step of the tetraarylborate compound without separating; Injecting a single active point catalyst solution containing a group 4 transition metal; Injecting an aluminum compound solution; And Injecting ethylene; a method for producing an ethylene homopolymer or a copolymer of ethylene and «-olefin is provided.

Effects of the Invention

[37] The tetraaryl borate compound according to the present invention is used for a hydrocarbon-based solvent.

It has high solubility, excellent thermal stability, and uses a single active point catalyst even at high temperatures.

In particular, the tetraarylborate compound can be completely soluble in an aliphatic hydrocarbon-based solvent, so it may not be limited in its usage due to its solubility. In addition, the solution-type cocatalyst provided through it can operate a commercial process.

In addition to facilitating, it can be a means of solving the problem of using a cocatalyst provided in the form of dispersion or slurry, which is pointed out as a problem of the prior art.

[38] In addition, it can maintain high catalytic activity even at high temperatures, and ethylene, ₍ X-olefin, other

Since it has excellent co-polymerization reactivity with comonomers and the like and can produce high-molecular-weight polymers in high yield, its commercial practicality is high in combination with single active point catalysts such as various metallocenes or non-metallocenes.

[39] In addition, by limiting the degree of isomerization of (X-olefins of 04 or more during solution polymerization carried out at high temperatures, it is possible to effectively reduce the consumption of comonomers such as (X-olefins). In addition, economically, it has various physical properties. It is possible to provide a high molecular weight ethylene-based polymer, that is, an ethylene-based polymer such as an ethylene homopolymer or a copolymer of ethylene and (X-olefin).

Best mode for carrying out the invention

[4] Hereinafter, the present invention will be described more specifically. If there is no other definition in the technical and scientific terms used at this time, it has the meaning that a person who has ordinary knowledge in the technical field to which this invention belongs is usually understood, In the following description, a description of a notification function and configuration that may unnecessarily obscure the gist of the present invention will be omitted.

[41] The term "alkyl" used in the present specification means a monovalent linear or branched saturated hydrocarbon radical composed of only carbon and hydrogen atoms. Examples of such alkyl include methyl, ethyl, propyl, butyl, pentyl, nuclears, heptyl, Including, but not limited to, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc.

[42] The term "aryl" in this specification is aromatic by the removal of one hydrogen.

Organic radicals derived from hydrocarbons, suitable for each ring 4 to 7, 2020/174346 5 ?€1/162020/051519

Preferably, it includes a single or fused ring system containing ₅ or 6 ring atoms, and includes a form in which a plurality of aryls are connected by a single bond. The fused ring system may contain an aliphatic ring such as a saturated or partially saturated ring, and must contain one or more aromatic rings. The aliphatic ring also contains nitrogen, oxygen, sulfur, carbonyl, etc. in the ring. Examples of the aryl radical include phenyl, naphthyl, biphenyl, indenyl, fluorenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrycenyl, naphthacenyl,

9, 10 -dihydroanthracenyl, etc., including but not limited to.

[43] The term "cycloalkyl" as used herein refers to a monovalent saturated carbocyclic radical composed of one or more rings. Examples of cycloalkyl radicals are

Cyclopropyl, cyclobutyl, cyclopentyl, cyclonuxyl, cycloheptyl, etc.

Including, but not limited to.

[44] The terms "halo" or "halogen" used in this specification mean fluorine, chlorine, bromine or iodine atoms.

[45] The term "haloalkyl" used herein refers to an alkyl substituted with one or more halogens, and examples include, but are not limited to, trifluoromethyl.

[46] The term "fluorine substituted aryl" in this specification means that one or more fluorine atoms

It means substituted aryl, where "aryl" is as defined above.

[47] As used herein, the term "arylalkyl" refers to alkyl substituted with one or more aryls.

It means, for example, but not limited to benzyl.

[48] The terms "alkoxy" and "aryloxy" used in this specification mean *-0 -alkyl radical and *-0 -aryl radical, respectively, where "alkyl" and "aryl" are as defined above.

[49] The term "catalyst activator" in this specification can be interpreted as having the same meaning as a co-catalyst, and the catalyst activator specifically described in this specification may be a compound represented by the following formula (1).

[5] For the activation of this single active point catalyst, the catalyst activator containing an ionic salt

They usually take the form of ionic salts. Due to these structural features, they are very insoluble in aliphatic hydrocarbon-based solvents and are soluble only to a small extent in aromatic hydrocarbon-based solvents.

[51] Furthermore, monomers for the production of ethylene-based polymers such as ethylene homopolymers or copolymers of ethylene and (X-olefin) are aliphatic in order to reduce the miscibility with solvents and the content of aromatic hydrocarbons in the resulting ethylene-based polymer. Although it is preferable to carry out the polymerization in a hydrocarbon-based solvent, the above-described problem has forced the use of an aromatic hydrocarbon-based solvent.

[52] In addition, when an aromatic hydrocarbon-based solvent such as toluene is used, the resulting high molecular weight ethylene homopolymer or a copolymer of ethylene and (X-olefin) remains in the resulting inferior polymer properties or an unpleasant odor. 2020/174346 6 ?€1/162020/051519

[53] As a result of research on catalyst activators containing ionic salts capable of solution polymerization in aliphatic hydrocarbon-based solvents, the applicant of the present invention, focusing on the problems of these conventional technologies, has resulted in a new cation having an alkylidene anilinium structure. The tetraarylborate compound was designed.

[54] tetraarylborates having a cation having such an alkylideneanilinium structure

The compound has a high solubility in both linear aliphatic hydrocarbon-based solvents as well as cyclic aliphatic hydrocarbon-based solvents. Therefore, it is suitable for use in continuous solution processes where it is necessary to control a specific amount of catalyst activator. In particular, when it contains it

«- Effectively limits the isomerization of olefins.

[55] In addition, the tetraarylborate compound having an alkylidene anilinium structure cation has excellent high-temperature stability, so it exhibits excellent effects on catalyst activation even at high temperature polymerization temperatures of 160° or higher, and makes it possible to operate commercially, so it is used industrially. The value is high.

[56] Hereinafter, a tetraaryl borate compound according to the present invention and a catalyst comprising the same

The composition will be described in detail.

[57] The tetraaryl borate compound according to an embodiment of the present invention may be represented by the following formula (1).

3 30) cycloalkyl, ((：1 30) alkyl 6 30) aryl, (6 30) aryl,

(06 30) Aryloxy, ((：1 30) Alkyl (06 30) Aryloxy, (06 30) Aryl(0 30) Alkyl and ((0-030) Alkyl 6 30) Aryl) ((1 30) It may be further substituted with one or more substituents selected from alkyl, etc.]

[66] As described above, the tetraaryl borate compound has the use of a catalyst activator for activating the main catalyst for the production of an ethylene homopolymer or a copolymer of ethylene and (X-olefin). Specifically, the tetraaryl borate compound has the use of a catalyst activator. The compound is an aliphatic hydrocarbon system improved by containing a cations of an alkylidene anilinium structure. 2020/174346 7 ?€1/162020/051519

Solubility in the solvent is realized. Thus, ethylene homopolymer or ethylene and

«- It shows improved catalytic activity under the conditions of solution polymerization under an aliphatic hydrocarbon-based solvent for the production of copolymers of olefins, especially under continuous solution polymerization conditions.

[67] Specifically, the tetraarylborate compound is the following formula (2) or

It may be represented by Chemical Formula 3.

[Formula 2]

[70] [In Chemical Formula 2,

[Group] The above 瓦 II ^{1 and} John ² are the same as the definition in Formula 1 of claim 1;

[72] II ¹¹ to II ¹⁵ are each independently hydrogen, (0 30) alkyl, halo ((：1 30) alkyl or (06 30) aryl((：1 30) alkyl.]

[Formula 3]

[74]

[In Chemical Formula 3,

Above: 8 is the same as the definition in Formula 1 of claim 1;

II ¹¹ to II ¹⁵ are each independently hydrogen, (0-030) alkyl, halo ((:1 30) alkyl, or 979 56 88 (06 30) aryl((:1 30) alkyl;

7777 766 8 ⁷³

II is an integer selected from 2 to 6;

II ²¹ and II ²² are each independently hydrogen, (0 30) alkyl, (0^30) alkoxy, halo (0 30) alkyl, 3 30) cycloalkyl, (0 30) alkyl 6 30) aryl,

(06 30) aryl, 6 30) aryloxy, (0 30) alkyl 6 30) aryloxy,

（6 30）aryl（（：1 30）alkyl or（片1 30）alkyl（6 30）aryl）（（：1 30）alkyl.]

80] More specifically, in Formula 1, at least one selected from II 1 and II ^{2 may be} a long-chain alkyl, that is, (8 30) alkyl.

For example, in Formula 2, II ¹¹ to II ¹⁵ are each independently hydrogen or (0 30) alkyl; II ¹ and! At least one selected from 1 ^{2 may be} a long-chain alkyl, wherein II ¹ hydrogen or 片8 30) alkyl, and II ² may be ((:1 30) alkyl.

82] For example, in Chemical Formula 2, II ¹¹ to II ¹⁵ are each independently hydrogen or

((：1 7) is alkyl; at least one selected from II ¹ and! 1 ² is a long-chain alkyl, wherein II ^{1 is} hydrogen or 片8 30) alkyl, and II ² is 片8 30) alkyl. Thing 2020/174346 8 ?€1/162020/051519

Can

[83] For example, in Chemical Formula 2, II ¹¹ to II ¹⁵ are each independently hydrogen, methyl or ethyl; At least one selected from Yo! and Yo ² is a long-chain alkyl, and II ¹ hydrogen or ( 8 30) alkyl, and II ² may be (8 30) alkyl.

[84] As an example, in Chemical Formula 3, II ¹¹ to II ¹⁵ are each independently hydrogen or

（（：1 30）alkyl; II is an integer selected from 2 to 4; The elements ²¹ and II ²² may each independently be hydrogen or (08-030) alkyl.

[85] As an example, in Chemical Formula 3, II ¹¹ to II ¹⁵ are each independently hydrogen or

((：1 7) is alkyl; said II is an integer of 3 or 4; said i and II ²² are each independently hydrogen or 8 30) may be alkyl.

[86] As an example, in Chemical Formula 3, II ¹¹ to II ¹⁵ are each independently hydrogen or

（（：1 7）alkyl; The above II is an integer of 3 or 4; The above and II ²² may each independently be hydrogen or ((：1 7) alkyl.

[87] As an example, in Formula 3, II ¹¹ to II ¹⁵ are each independently hydrogen, methyl or ethyl, and II is an integer of 3 or 4, and II ²¹ and II ²² are each independently hydrogen or (8 30) May be alkyl.

[88] Most specifically, in Chemical Formula 1, II ¹ and II ² are each independently

(02 30) May be alkyl.

As an example, in Formula 2, II ¹¹ to II ¹⁵ are each independently hydrogen, methyl or ethyl; 1^ 1 and ² may be (02 30) alkyl.

[9 As an example, Formula 3 is II ¹¹ to II ¹⁵ are each independently hydrogen, methyl or ethyl, and II is an integer of 3 or 4, and II ²¹ and II ²² are each independently hydrogen or (02^30) alkyl, and at least one of II ²¹ and II ²² is

(02 30) May be alkyl.

[91] As an example, in Chemical Formula 1, II ¹ is (05-025), and II ² is

(06-026) May be alkyl.

[92] For example, in Chemical Formula 1, II is ((：15-(：17)), and II ² is

(06-08) May be alkyl.

[93] In addition, one specific compound of the tetraarylborate compound represented by Formula 1 is methyl-methylideneanilinium tetrakis (pentafluorophenyl) borate, 4 -methyl-N-octadecyl-N-octade Silideneanilinium

Tetrakis (pentafluorophenyl) borate, butyl-butylideneanilinium tetrakis (pentafluorophenyl) borate,

Tetradecyl-tetradecylideneanilinium tetrakis (pentafluorophenyl) borate, hexadecyl-hexadecylideneanilinium tetrakis (pentafluorophenyl) borate and octadecyl-N-octadecylideneanilinium

Tetrakis (pentafluorophenyl) borate, etc., but are not limited thereto. 2020/174346 9 ?€1/162020/051519

[94] Preferably, tetradecyl-tetradecylideneanilinium

Tetrakis (pentafluorophenyl) borate, hexadecyl-hexadecylideneanilinium tetrakis (pentafluorophenyl) borate,

4 -Methyl-N-octadecyl-N-octadecylideneanilinium tetrakis(pentafluorophenyl)borate and octadecyl-N-octadecylideneanilinium

Tetrakis (pentafluorophenyl) borate, etc., more preferably

Tetradecyl-tetradecylideneanilinium tetrakis (pentafluorophenyl) borate, hexadecyl-hexadecylideneanilinium tetrakis (pentafluorophenyl) borate and octadecyl-N-octadecylideneanilinium

And tetrakis (pentafluorophenyl) borate.

[95] The tetraarylborate compound according to an embodiment of the present invention may be used as a catalyst activator for preparing an ethylene homopolymer and an ethylene-based copolymer selected from ethylene and a copolymer of ethylene (X-olefin, etc.). Arylborate compounds have remarkably high solubility in aliphatic hydrocarbon-based solvents as well as aromatic hydrocarbon-based solvents. Furthermore, since they can be uniformly dissolved and used even in aliphatic hydrocarbon-based solvents, the realization of more improved catalytic activity is of course

Stable operation of the production process is possible.

[96] In addition, even if it is applied to the solution polymerization method carried out at a high temperature of 100 °0 or higher,

With stable catalytic activity, it can be advantageous for producing high molecular weight polymers.

In addition, the tetraarylborate compound according to an embodiment of the present invention may be prepared by reacting a compound represented by the following formula (4) and a compound represented by the following formula (5) in a hydrocarbon-based solvent. In this case, the tetraaryl borate compound may be prepared by reacting the compound represented by the following formula (5). The borate compound can be used as a catalyst activator without separation and purification.

[98] [Formula 1]

[99]

Love ^{1- +} Nasi 4

V

0 is [Chemical Formula 4]

_ Na's ₄

[102] [Formula 5]

[103]

一

2

[104] [In Formula 1, Formula 4, and Formula 5,

[105] 6 is a boron atom;

[106] Four ¹ is (06 30) aryl, and the aryl of the ^{first one} is selected from ((：1 30) alkyl, halo((：1 30) alkyl and (6 30) aryl(0 30) alkyl, etc. May be further substituted with more than one substituent; 2020/174346 10 ?€1/162020/051519

[107] four ² is a fluorine substituted (6 30) aryl;

[108] element ¹ is hydrogen or ((：1 30) alkyl;

[109] II is ((：1 30) alkyl, but the number of carbons in II is one greater than the number of carbons in II'£]

It has a carbon number, and in the case of II ¹ dihydrogen, its carbon number is 0;

[110] 11 ² is ((：1 30) alkyl, or can be linked to II ¹ to form a ring, and the ring is (0 30) alkyl, (0 30) alkoxy, halo((：1 30) alkyl ,(0030)cycloalkyl, (()1 30)alkyl(6 30)aryl,(06 30)aryl,(06 30)aryloxy,

（（：1 30）alkyl（6 30）aryloxy,（6 30）aryl（（：1 30）alkyl and

((0 30) Alkyl (6 30) Aryl) (0 30) May be further substituted with one or more substituents selected from alkyl.]

[111] As an example, the hydrocarbon-based solvent is 11-pentane, pentane, !!-nucleic acid, nucleic acid, 11-heptane, 1-heptane, 11-octane, octane, 11-nonane, nonane, 11-decane and decane, etc. Selected linear aliphatic hydrocarbon-based solvent; Cyclic aliphatic hydrocarbon-based solvent selected from cyclopentane, cyclonucleic acid, methylcyclonucleic acid, dimethylcyclonucleic acid, ethylcyclonucleic acid, imentane and decahydronaphthalene; and benzene, toluene, xylene, etc. It may be one or two or more mixed solvents selected from aromatic hydrocarbon-based solvents.

[112] As an example, the reaction may be carried out under a temperature condition of 0 to 50 o (:.

As an example, the reaction may be performed for 10 to 120 minutes, but is not limited as long as it is a point at which the solution in a dispersed or slurry state is completely dissolved during the reaction.

As described above, the tetraarylborate compound according to an embodiment of the present invention exhibits an excellent effect in activating a single active point catalyst. Specifically, the single active point catalyst may be a metallocene catalyst.

[115] For example, the single active point catalyst may contain a transition metal of Group 4 on the periodic table, and these transition metals may exist in a +2, +3, or +4 type oxidation state.

[116] As an example, a ligand suitable for the single active point catalyst is anionic non-localized

-It may include a bonded group, and the anionic delocalized -bonded group may include a cyclic compound selected from cyclopentadienyl derivatives, indenyl derivatives and fluorenyl derivatives.

[117] Specifically, the transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and «-olefin according to an embodiment of the present invention is described above.

Tetraarylborate compounds; It may contain a single active point catalyst containing a group 4 transition metal; and an aluminum compound.

[118] More specifically, the single active point catalyst may be represented by the following chemical formula. This is a transition metal compound based on an indenyl ((1¥, etc.) group introduced with a nitrogen-containing substituent, and is the core metal as the 4 in the periodic table. The foot transition metal has a solid (]) planar structure, rich in electrons and widely delocalized, and has a structure connected by an indene or its derivative introduced with a nitrogen-containing substituent; an amido group substituted with a silyl group; In particular, indene or its nitrogen-containing substituent 2020/174346 11 ?€1/162020/051519

The silyl group connecting the derivative group and the amido group contains both an alkyl group or an alkenyl group and an aryl group that induces a narrow molecular weight distribution rather than a wide molecular weight distribution, which is a disadvantage of diastereomerism and improved solubility in general hydrocarbon-based solvents. It has the structural characteristics of the present invention, and is advantageous in obtaining an ethylene-based copolymer having an increased catalyst efficiency and high molecular weight by combining with a catalyst activator or a catalyst activating composition according to the present invention at high temperatures.

[121] [In the above formula show,

[122] M is a transition metal of Group 4 on the periodic table;

[123] II _! Is ((：1 30) alkyl or (2 20) alkenyl, and the group II alkyl or alkenyl is one or more selected from halogen, (6 30) aryl and ((:1 30) alkyl (6 30) aryl, etc. May be further substituted with a substituent;

[124] Buy _! Is (06 30) aryl, and the above _! £]aryl may be further substituted with one or more substituents selected from ((：1 30) alkyl, halo(0 30) alkyl and (6 30) aryl(0 30) alkyl;

[125] II ₂ to II ₅ are each independently hydrogen, (0 30) alkyl, (0 30) alkoxy,

Halo(0 30) alkyl, 3 20) cycloalkyl, (0 30) alkyl 6 30) aryl,

(06 30) aryl, 6 30) aryloxy, (0 30) alkyl 6 30) aryloxy,

（6 30）aryl（0 30）alkyl or

（（0 30）alkyl（6 30）aryl）（0 30）alkyl, or the 11 ₂ to 11 ₅ can be linked with adjacent substituents to form a fused ring, and the fused ring is (0 30) alkyl, （0 30) alkoxy, halo (0 30) alkyl, (3 20) cycloalkyl,

（（）1 30）alkyl（6 30）aryl,（06 30）aryl,（06 30）aryloxy,

（（：1 30）alkyl（6 30）aryloxy,（6 30）aryl（（：1 30）alkyl and

((0 30) alkyl( 6 30) aryl) (0 30) may be further substituted with one or more substituents selected from alkyl and the like;

[126] II ₉ is ((:1 30) alkyl, 3 20) cycloalkyl or (6 30) aryl ((:1 30) alkyl;

[127] Yo ^ and II ₇ are each independently (0 30) alkyl, halo (0 30) alkyl,

3 20) Cycloalkyl, (6 30) aryl, ((1 30) alkyl (06 30) aryl,

（（：1 30）alkoxy（6 30）aryl or（6 30）aryl（0 30）alkyl, or the above ₆ and II ₇ can be linked to each other to form a ring, and the ring is（（：1 30） Alkyl, Halo (C1-C30)alkyl, (C6-C30)aryl (C1-C30)alkyl, (C1-C30)alkoxy,

(C3-C20)cycloalkyl, (C6-C20)aryl, (C1-C30)alkyl (C6-C30)aryl and

May be further substituted with one or more substituents selected from (C6-C20)aryloxy and the like;

[128] R ₈ is hydrogen or (C1-C30)alkyl;

[129] X 1 and X ₂ are each independently halogen, (C1-C30)alkyl, (C2-C20)alkenyl,

(C3-C20)cycloalkyl, (C6-C30)aryl, (C6-C30)aryl (C1-C30)alkyl,

((C1-C30)alkyl (C6-C30)aryl) (C1-C30)alkyl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C1-C30)alkyl (C6-C30)aryloxy, (C1-C30)alkoxy (C6-C30)aryloxy, -OSiR ^a R ^b R ^c , -SR ^d , -NR ^e R ^f , -PR ^g R ^h or (C1-C30)alkylidene;

[13 wherein R ^a to R ^d are each independently (C1-C30)alkyl, (C6-C20)aryl,

(C6-C20)aryl (C1-C30)alkyl, (C1-C30)alkyl (C6-C20)aryl or

(C3-C20)cycloalkyl;

[131] R ^e to R ^h are each independently (C1-C30)alkyl, (C6-C20)aryl,

(C6-C20)aryl (C1-C30)alkyl, (C1-C30)alkyl (C6-C20)aryl, (C3-C20)cycloalkyl, tri (C1-C30)alkylsilyl or tri (C6-C20)aryl Silyl;

[132] However, if one of X i or X ₂ is (C1-C30)alkylidene, the other is ignored.]

[133] The indene-based transition metal compound of the present invention is a single active point catalyst having a structural characteristic including an alkyl group or an alkenyl group and an aryl group at the same time in the silyl group connecting the indenyl group and the amido group into which a nitrogen-containing substituent is introduced. And an aryl group having good injectability of an alkyl group or an alkenyl group and a higher alpha-olefin which is advantageous in terms of solubility. In addition, there are two structural features including an alkyl group or an alkenyl group and an aryl group at the same time in the silyl group. of

The presence of diastereomers was confirmed by H ⁱ -NMR. The catalysts developed in the present invention were produced in a ratio of 1:1 to 1:8 despite the presence of diastereomers, and a polymer having a narrow molecular weight distribution was produced, and at high temperatures. In addition, it exhibits properties such as high activity, and is more synergistic when combined with the catalyst activator or catalytic activator composition of the present invention described above. Conventionally, indenyl groups and amido groups have diastereomers connected by silyl groups. It has been reported that the molecular weight distribution has a wide characteristic. However, when the indene-based transition metal compound of the present invention is used in combination with a catalyst activator or a catalytic activator composition, an ethylene-based copolymer with a narrower molecular weight distribution is obtained at high temperatures. In particular, by various combinations with the above-described catalyst activator or catalyst activator composition, the formation of isomers that make polymerization control difficult is suppressed, and the molecular weight distribution is narrow and the composition composition is narrow. Ethylene-based copolymers of molecular weight can be obtained, and the molecular weight distribution is narrow.

Chemical Composition Distribution can be said to be of great commercial value because it can obtain an ethylene-based copolymer with a wide range of properties.

[134] According to an embodiment of the present invention, ethylene homopolymer or of ethylene and a-olefin 2020/174346 13 ?€1/162020/051519

In the transition metal catalyst composition for preparing a copolymer, the indene-based transition metal compound of the above chemical formula may be represented by the following formula: 8:

[137] [In Chemical Formula: 8,

;

(03 7) Alkylene with or without adjacent substituents and aromatic rings,

(03 7) Alkenylene or 4 7) Alkadienylene can form a fused ring, and the fused ring is (0 30) alkyl, (0 30) alkoxy, halo ((:1 30) alkyl, 3 20) Cycloalkyl, ((1 30) alkyl 6 30) aryl, (06 30) aryl,

(06 30) Aryloxy, ((：1 30) Alkyl (06 30) Aryloxy, (06 30) Aryl(0 30) Alkyl and ((0-030) Alkyl 6 30) Aryl) ((1 30) May be further substituted with one or more substituents selected from alkyl and the like;

[14, II„ to II ₁₅ are each independently hydrogen, (0 30) alkyl, halo ((:1 30) alkyl or

（06 30）Aryl（（：1 30）alkyl.]

[141] Ethylene homopolymer or ethylene and (X-olefin according to an embodiment of the present invention)

In the transition metal catalyst composition for preparing a copolymer, the indene-based transition metal compound of the above chemical formula is a transition metal of Group 4 on the periodic table, specifically titanium (1¾, zirconium ()·) or hafnium^! ⁷ ）Can be, and more specifically, titanium (II) or zirconium ]·).

[142] The above (0 30) alkyl group, for example, methyl group, ethyl group, II-propyl group, isopropyl group, 11-butyl group, isobutyl group, -butyl group, butyl group, 11-pentyl group, neo Pentyl group, amyl group,

11-nuclear group, II-octyl group, II-decyl group, II-dodecyl group or !!-pentadecyl group; The (2 20) alkenyl group is, for example, a vinyl group or an allyl group;

(3 20) Cycloalkyl group, for example, cyclopropyl group, cyclobutyl group, It is a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, or a cyclododecyl group; the (C6-C30) aryl group or

(C1-C30) Alkyl (C6-C30) aryl group, for example, a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2, 3-xylyl group, 2, 4 -xylyl group, 2, 5 -xylyl group, 2, 6 -xylyl group, 3, 4 -xylyl group,

3.5 -xylyl group, 2, 3, 4 -trimethylphenyl group, 2, 3, 5 -trimethylphenyl group,

2, 3, 6-trimethylphenyl group, 2, 4, 6-trimethylphenyl group, 3, 4, 5-trimethylphenyl group,

2.3.4.5 -tetramethylphenyl group, 2, 3, 4, 6 -tetramethylphenyl group, 2, 3, 5, 6 -tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, _n _propylphenyl group, isopropylphenyl group, _n- Butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group,

Biphenyl group, fluorenyl group, triphenyl group, naphthyl group or anthracenyl group; The (C6-C30) aryl (C1-C10) alkyl group or

((C1-C30) alkyl (C6-C30) aryl) (C1-C30) alkyl group, for example, benzyl group,

(2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group,

(2, 3 -dimethylphenyl) methyl group, (2, 4 -dimethylphenyl) methyl group, (2, 5 -dimethylphenyl) methyl group,

(2, 6 -dimethylphenyl) methyl group, (3, 4 -dimethylphenyl) methyl group, (4, 6 -dimethylphenyl) methyl group,

(2, 3, 4-trimethylphenyl) methyl group, (2, 3, 5-trimethylphenyl) methyl group,

(2, 3, 6-trimethyl-phenyl) methyl group, (3, 4, 5-trimethylphenyl) methyl group,

(2, 4, 6-trimethylphenyl) methyl group, (2, 3, 4, 5-tetramethylphenyl) methyl group,

(2, 3, 4, 6 -tetramethylphenyl) methyl group, (2, 3, 5, 6 -tetramethylphenyl) methyl group,

(Pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group,

(Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group,

(Tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group,

( _N -Hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group,

(N-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, or

Anthracenylmethyl group; the (C1-C30) alkoxy group, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group,

tert-butoxy group, n-pentoxy group, neopentoxy group, n-nuclear group, n-octoxy group, n-dodecyl group, n-pentadesoxy group, or _n -eicosoxy group.

[143] According to an embodiment of the present invention, ethylene homopolymer or of ethylene and a-olefin

In the transition metal catalyst composition for preparing a copolymer, in the indene-based transition metal compound of Formula B, R ₆ and R ₇ are each independently (C1-C30) alkyl,

(C3-C20) cycloalkyl or (C6-C30) aryl, or the above 11 ₆ and 11 ₇ can be linked by (C3-C7) alkylene with or without aromatic rings to form a ring, and the formed ring Is (C1-C30) alkyl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkoxy, (C3-C20) cycloalkyl, (C6-C20) aryl, (C1-C30) alkyl ( C6-C30) aryl and

It may be further substituted with one or more selected from the group consisting of (C6-C20) aryloxy and the like. 2020/174346 15 ?€1/162020/051519

[144] According to an embodiment of the present invention, ethylene homopolymer or ethylene and (X-olefin

In the transition metal catalyst composition for preparing a copolymer, in the indene-based transition metal compound of the above chemical formula, II ((：1 30) alkyl, (2 20) alkenyl or

(6 30) aryl ((1 30) alkyl and the number of days; _four! Silver（6 30）aryl or

(0 30) Alkyl 6 30) _May be aryl; the II ₂ to II ₅ are each independently hydrogen, ((1 30) alkyl, ((1 30) alkoxy, (0-030) alkyl 6 30 ）Aryl,（ 6 30）aryl, （6 30）aryloxy, （（：1 30）alkyl（ 6 30）aryloxy or

(06-030) aryl ((：1 30) alkyl, or II ₂ to II _{5 above} are (03 7) alkylene, 3 7) alkenylene or (04 7) with or without adjacent substituents and aromatic rings ）Can form a fusion ring by connecting with alkadienylene,

The fused ring is (0 30) alkyl, (0 30) alkyl 6 30) aryl, (06 30) aryl,

It may be further substituted with one or more substituents selected from (06^30) aryl ((：1 30) alkyl and (片 1 30) alkyl (6 30) aryl) (0 30) alkyl; the above II ₉ is ((：1) 30) alkyl, (03^20) cycloalkyl or 片6 30) aryl (0 30) alkyl; the 11 ₆ and 11 ₇ are each independently (0 30) alkyl, (0020) cycloalkyl, 片 6 30) Aryl,

（（：1 30）alkyl（6 30）aryl,（0 30）alkoxy（6 30）aryl or

（6 30）aryl（（：1 30）alkyl, or the above II ₆ and II ₇ may be linked by alkylene with or without aromatic ring (03 7) to form a ring, and the ring is (0- 030) Alkyl, 6 30) Aryl (0 30) Alkyl, (0 30) Alkoxy, (0020) Cycloalkyl, (6 20) Aryl, ((:1 30) Alkyl (6 30) Aryl and (6 20) It may be further substituted with one or more substituents selected from aryloxy and the like; and II ₈ may be hydrogen or (0 30) alkyl.

[145] According to an embodiment of the present invention, ethylene homopolymer or ethylene and (X-olefin

In the transition metal catalyst composition for preparing a copolymer, in the indene-based transition metal compound of the above chemical formula, II ₁ is more specifically a methyl group, ethyl group, ₁₁ -propyl group, isopropyl group, II -butyl group, vinyl group, allyl group Or it may be a benzyl group; above shows] ₁ is more specifically a phenyl group, naphthyl group, biphenyl group, tolyl group, trimethylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, octylphenyl group, decylphenyl group, dodecylphenyl group or

It may be a tetradecylphenyl group; The II ₂ to II ₅ are each independently hydrogen, methyl group, ethyl group, II -propyl group, isopropyl group, II -butyl group, phenyl group, naphthyl group, biphenyl group,

2 -isopropylphenyl group, 3,5 -xylyl group, 2, 4, 6 -trimethylphenyl group, benzyl group, methoxy group, ethoxy group, isopropoxy group, phenoxy, 4 or -butylphenoxy group or naphthoxy group Or

It can be connected to form a fusion ring, and the 11 ₂₁ to 11 ₂₄ are each independently hydrogen, methyl group, ethyl group, _I! -Propyl group, isopropyl group, ₁₁ -butyl group, isobutyl group, 2020/174346 16 ?€1/162020/051519

2-methylbutyl group, 8-butyl group, butyl group, 11-pentyl group, neopentyl group, amyl group, 11-nuclear group,

11-octyl group, 11-decyl group, 11-dodecyl group, 11-pentadecyl group, phenyl group, 2 -tolyl group, 3 -tolyl group,

4-tolyl group, 2, 3 -xylyl group, 2, 4 -xylyl group, 2, 5 -xylyl group, 2, 6 -xylyl group, 3, 4 -xylyl group,

3.5 -xylyl group, 2, 3, 4 -trimethylphenyl group, 2, 3, 5 -trimethylphenyl group,

2.3.6-trimethylphenyl group, 2, 4, 6-trimethylphenyl group, 3, 4, 5-trimethylphenyl group,

2.3.4.5 -tetramethylphenyl group, 2, 3, 4, 6 -tetramethylphenyl group, 2, 3, 5, 6 -tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, ^propylphenyl group, isopropylphenyl group, _!1- Butylphenyl group, yo-butylphenyl group, 1631-butylphenyl group, II-pentylphenyl group, neopentylphenyl group, II-hexylphenyl group, 11-octylphenyl group, 11-decylphenyl group, 11-dodecylphenyl group, 11-tetradecylphenyl group, non Phenyl group, florenyl group, triphenyl group, naphthyl group, anthracenyl group, benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2, 3-dimethylphenyl) methyl group,

(2, 4 -dimethylphenyl) methyl group, (2, 5 -dimethylphenyl) methyl group, (2, 6 -dimethylphenyl) methyl group,

(3, 4 -dimethylphenyl) methyl group, (4, 6 -dimethylphenyl) methyl group, (2, 3, 4 -trimethylphenyl) methyl group,

(2, 3, 5 -trimethylphenyl) methyl group, (2, 3, 6 -trimethylphenyl) methyl group,

(3, 4, 5 -trimethylphenyl) methyl group, (2,4, 6 -trimethylphenyl) methyl group,

(2, 3, 4, 5 -tetramethylphenyl) methyl group, (2, 3, 4, 6 -tetramethylphenyl) methyl group,

(2, 3, 5, 6 -tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, chi-propylphenyl) methyl group, (isopropylphenyl) methyl group, chi-butylphenyl) methyl group,

(8^-butylphenyl) methyl group, (1631 -butylphenyl) methyl group, 知-pentylphenyl) methyl group,

(Neopentylphenyl) methyl group, (11-hexylphenyl) methyl group, 知-octylphenyl) methyl group,

(11-decylphenyl) methyl group, 知-decylphenyl) methyl group, (11-tetradecylphenyl) methyl group,

It may be a naphthylmethyl group or an anthracenylmethyl group; 11 ₉ is an isopropyl group,

11-butyl group, isobutyl group, 2-methylbutyl group, ₈ -butyl group, butyl group, 11-pentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, benzyl group or diphenylmethyl group; II ^ and II ₇ are each independently a methyl group, an ethyl group, a II-propyl group,

Isopropyl group, 11-butyl group, isobutyl group, 2-methylbutyl group, -butyl group, 1631-butyl group,

11-pentyl group, neopentyl group, amyl group, 11-nuclear group, ！！-octyl group, 11-decyl group, 11-dodecyl group,

11-pentadecyl group, phenyl group, 2 -tolyl group, 3 -tolyl group, 4 -tolyl group, 2, 3 -xylyl group, 2, 4 -xylyl group,

2.5-xylyl group, 2, 6-xylyl group, 3, 4-xylyl group, 3, 5-xylyl group, 2, 3, 4-trimethylphenyl group,

2.3.5-trimethylphenyl group, 2, 3, 6-trimethylphenyl group, 2, 4, 6-trimethylphenyl group,

3.4.5 -trimethylphenyl group, 2, 3, 4, 5 -tetramethylphenyl group, 2, 3, 4, 6 -tetramethylphenyl group,

2.3.5.6 -Tetramethylphenyl group, pentamethylphenyl group, epropylphenyl group, isopropylphenyl group, II-butylphenyl group, i-butylphenyl

, Phenyl group,

₁₁ -pentylphenyl group, neopentylphenyl group, II -hexylphenyl group, II -octylphenyl group, II -decylphenyl group,

11-dodecylphenyl group, II-tetradecylphenyl group, biphenyl, fluorenyl, triphenyl, naphthyl group, anthracenyl group, benzyl group, naphthylmethyl group, anthracenylmethyl group or \¥0 2020/174346 17 1»（ /182020/051519

Can be linked to form a ring; The 11 ₃₁ to 11 ₃₅ , 11 ₄₁ and 11 ₄₂ are each independently hydrogen, a methyl group, an ethyl group, _I! -Propyl group, isopropyl group, ₁₁ -butyl group, isobutyl group, 2 -methylbutyl group, 8 -butyl group, butyl group, II -pentyl group, neopentyl group, amyl group, II -nuxyl group, II- Octyl group, II -decyl group, II -dodecyl group, II -pentadecyl group, phenyl group,

2-tolyl group, 3-tolyl group, 4-tolyl group, 2, 3 -xylyl group, 2, 4 -xylyl group, 2, 5 -xylyl group,

2.6 -xylyl group, 3, 4 -xylyl group, 3, 5 -xylyl group, 2, 3, 4 -trimethylphenyl group,

2.3.5-trimethylphenyl group, 2, 3, 6-trimethylphenyl group, 2, 4, 6-trimethylphenyl group,

3.4.5 -trimethylphenyl group, 2, 3, 4, 5 -tetramethylphenyl group, 2, 3, 4, 6 -tetramethylphenyl group,

2.3.5.6 -Tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, II -propylphenyl group, isopropylphenyl group, II -butylphenyl group, i-butylphenyl group,

Butylphenyl group,

_11-pentyl group, a neopentyl group, a _II-haeksil group, _II-octyl group, a _II-decyl group,

11-dodecylphenyl group, II-tetradecylphenyl group, biphenyl group, fluorenyl group, triphenyl group, naphthyl group, anthracenyl group, benzyl group, naphthylmethyl group, or anthracenylmethyl group; the III and II are each independently 1 And II ₈ may be hydrogen, methyl group, ethyl group, 11-propyl group, isopropyl group -butyl group, isobutyl group, 2-methylbutyl group or ₈ -butyl group.

[146] In the definitions of X ₁ and X ₂ , the halogen atom may be exemplified by a fluorine, chlorine, bromine or iodine atom, and the (0 30) alkyl group is a methyl group, an ethyl group, II-propyl group, isopropyl group, 11- Butyl group, ₈ -butyl group, butyl group, 11-pentyl group, neopentyl group, amyl group, 11-nuxyl group, II-octyl group, II-decyl group, II-dodecyl group, II-pentadecyl group or! ！- may be exemplified by an eicosyl group; 3 20) The cycloalkyl group may be exemplified by a cyclopropane group, a cyclobutyl group, a cyclopentyl group, a cyclohexanyl group, a cycloheptyl group or an adamantyl group; the above (6 30 ）Aryl group may be exemplified by a phenyl group or a naphthyl group; the above (6 30) aryl ((：1 30) an alkyl group

（（（： 1 30）alkyl（6 30）aryl）（（： 1 30）alkyl group is benzyl group, (2-methylphenyl) methyl group,

(3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2, 3-dimethylphenyl) methyl group,

(2, 4 -dimethylphenyl) methyl group, (2, 5 -dimethylphenyl) methyl group, (2, 6 -dimethylphenyl) methyl group,

(3, 4 -dimethylphenyl) methyl group, (4, 6 -dimethylphenyl) methyl group, (2, 3, 4 -trimethylphenyl) methyl group, 2020/174346 18 ?€1/162020/051519

(2, 3, 5 -trimethylphenyl) methyl group, (2, 3, 6 -trimethyl-phenyl) methyl group,

(3, 4, 5 -trimethylphenyl) methyl group, (2,4, 6 -trimethylphenyl) methyl group,

(2, 3, 4, 5 -tetramethylphenyl) methyl group, (2, 3, 4, 6 -tetramethylphenyl) methyl group,

(2, 3, 5, 6 -tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, chi-propylphenyl) methyl group, (isopropylphenyl) methyl group, chi-butylphenyl) methyl group,

(8^-butylphenyl) methyl group, _£] 1-butylphenyl) methyl group, 知-pentylphenyl) methyl group,

(Neopentylphenyl) methyl group, (11-hexylphenyl) methyl group, 知-octylphenyl) methyl group,

(11-decylphenyl) methyl group, 知-decylphenyl) methyl group, (11-tetradecylphenyl) methyl group,

It may be exemplified by naphthylmethyl group or anthracenylmethyl group; the (0 30) alkoxy is a methoxy group, an ethoxy group, an 11-propoxy group, an isopropoxy group, an 11-butoxy group, an 8-butoxy group, a 1631-butoxy group , II-pentoxy group, neopentoxy group, II-nuclear group, II-octoxy group, II-dodecoxy group,! _! -Pentade deception or _!! -It can be exemplified as an Echo period;

(06-030) Aryloxy may be exemplified by a phenoxy group, a 4-]1-butylphenoxy group, or a 4-methoxyphenoxy group; Examples of -0^11 ¾ ¾。 include a trimethylsiloxy group,

Triethylsiloxy group, tri-propylsiloxy group, triipropylsiloxy group,

Tri-11-butylsiloxy group, tri-8-butylsiloxy group, tri-butylsiloxy group,

-Pentylsiloxy group, tri- _! -Hexylsiloxy group or tricyclohexylsiloxy group, and examples of -NR ^e R ^f are dimethylamino group, diethylamino group, di-!!-propylamino group,

Diisopropylamino group, di-!！-butylamino group, di-8-butylamino group,

Dibutylamino group, diisobutyla

Propyl amino group, di- _!! -Hexylamino group, dioctylamino group, di-decylamino group, diphenylamino group, dibenzylamino group, methylethylamino group, methylphenylamino group, benzyl hexylamino group, bistri

There is; above -Mo! ! Examples of the dimethyl phosphine group, diethyl phosphine group,

Di-!！-propylphosphine group, diisopropylphosphine group, di-！！-butylphosphine group,

Di-8% -butylphosphine group, di-

Butylphosphine group, diisobutylphosphine group,

1 butylisopropylphosphine group, di-!！-hexylphosphine group, di-!！-octylphosphine group, di-!！-decylphosphine group, diphenylphosphine group, dibenzylphosphine group, methylethylphosphine group, Methylphenylphosphine group, benzyl hexylphosphine group, bistrimethylsilylphosphine group, or bis-1631-butyldimethylsilylphosphine group; Examples of -811- above are

Methylthio group, ethylthio group, propylthio group, isopropylthio group, 1-butylthio group, or isopentylthio group.

[147] According to an embodiment of the present invention, ethylene homopolymer or ethylene and (X-olefin

In the transition metal catalyst composition for preparing a copolymer, in the indene-based transition metal compound of the formula: 8, specifically, X ₁ and X ₂ are each independently halogen, ((1 30) alkyl, 3 20) cycloalkyl, （06 30）aryl,（06 30）aryl（0 30）alkyl, （（：1 30）alkoxy, （6 30）aryloxy ,（（：1 30）alkyl（ 6 30） Aryloxy,-F ¾ ¾ 2020/174346 19 ?€1/162020/051519

'Yo Yo ¾ or Middle Yo ¾ ¹¹ ; Said II-II ¹¹ may be independently (0 30) alkyl or 片 6 20) aryl.

[148] In the transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and (X-olefin according to an embodiment of the present invention), more specifically in the indene-based transition metal compound of Formula 8, X ₁ and X ₂ is independently fluorine, chlorine, bromine, methyl group, ethyl group, isopropyl group, amyl group, benzyl group, methoxy group, ethoxy group,

Nylamino group, dimethylphosphine group, diethylphosphine group, diphenylphosphine group, ethylthio group or

It may be an isopropylthio group.

[149] In the transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and (X-olefin according to an embodiment of the present invention), in the indene-based transition metal compound of Formula 8, most specifically, the silver tetravalent Titanium, zirconium or hafnium; II ₁ is (0 30) alkyl; II „to II ₁₅ are each independently hydrogen or (0-030) alkyl; 11 ₂ to II ₅ are each independently hydrogen or

2020/174346 20 ?€1/162020/051519

And; The II ₃₁ to II ₃₅ , II ₄₁ and II ₄₂ are each independently hydrogen or (0^30)alkyl; The III and II are each independently an integer of 1 to 4; The II ₉ is (0 30) alkyl or (0020) cycloalkyl; wherein X 1 and ₂ are as described in the paragraph above; above, _¾ are each independently (0 30 ₎ alkyl or

6 20) May be aryl.

[15] The ethylene homopolymer or ethylene and (X-olefin according to an embodiment of the present invention

In the transition metal catalyst composition for preparing a copolymer, the indene-based transition metal compound of the above formula: 8 may be selected from compounds of the following structure, but is not limited thereto.

[152] [In the above structure,

[153] IV! is tetravalent titanium, zirconium or hafnium;

[154] X ₁ and X ₂ are each independently fluorine, chlorine, bromine, methyl group, ethyl group, isopropyl group, amyl group, benzyl group, methoxy group, ethoxy group, isopropoxy group, butoxy group, phenoxy group, 2020/174346 21 ?€1/162020/051519

4b6]1-butylpe

Dimethylamino group, diphenylamino group, dimethylphosphine group, diethylphosphine group, diphenylphosphine group, ethylthio group or isopropylthio group.]

[155] On the other hand, the indene-based transition metal compound according to the present invention is preferably an active catalyst component used in the production of an ethylene homopolymer and an ethylene-based polymer selected from copolymers of ethylene and (X-olefin). While cationizing the core metal by extracting the X _I or X ₂ ligand in the metal complex, an aluminum compound, a boron compound, or a mixture thereof that can act as an anion can act together as a cocatalyst. Various combinations of the above-described indene-based transition metal compound, the group activator or the group activator composition, and an aluminum compound, a boron compound, or a mixture thereof are also within the scope of the present invention.

[156] In the transition metal catalyst composition for manufacturing an ethylene homopolymer or a copolymer of ethylene and (X-olefin according to an embodiment of the present invention), the aluminum compound may be used as a cocatalyst, and specifically, the following chemical formula 0 or It may be one or two or more selected from the alumina oxide compound of the formula (I); an organic aluminum compound of the formula £; and an organic aluminum oxide compound of the chemical formula or formula 0;

[157] [Formula (:]

[158] （- ^ ₅₁ ）-0-） _?

[159] [Chemical Formula

[16 Lee (II ₅₁ ) 1-0-New (11 ₅₁ ) ₂

[161] [Formula ¾

[162] （II ₅₂ ） ₃ _ 1（¾,

[163] [Chemistry

[164] ₅₃ ) ₂ New 0111 ₅₄

[165] [Formula (3]

[166] 11 ₅必1（011 ₅₄ ） ₂

[167] [In the above chemical formula (: to geochemical formula (3,

[168] 11 ₅₁ is (0 30) alkyl, preferably a methyl group or an isobutyl group, and is an integer selected from 5 to 20; II ₅₂ and II ₅₃ are each independently ((：1 30) alkyl;

£ is hydrogen or halogen; ]· is an integer selected from 0 to 3; Yn ₅₄ is ((：1 30) alkyl or 片6 30) aryl.]

[169] The aluminum compound may be specifically, one or a mixture of two or more selected from alkylaluminoxane and organic aluminum.

[170] As a specific example that can be used as the aluminum compound,

As an alkyl aluminoxane, methyl aluminoxane, modified methyl aluminoxane, or

Tetraisobutylaluminoxane, etc.; as organic aluminum

Trimethylaluminum,triethylaluminum,tripropylaluminum, Trialkyl aluminum including triisobutyl aluminum and trihexyl aluminum; Dialkyl aluminum chloride including dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride and dihexyl aluminum chloride; methyl aluminum dichloride,

Ethyl aluminum dichloride, propyl aluminum dichloride,

Alkyl aluminum dichloride including isobutyl aluminum dichloride and hexyl aluminum dichloride; dimethyl aluminum hydride,

Diethyl aluminum hydride, dipropyl aluminum hydride,

Containing diisobutylaluminum hydride and dihexylaluminum hydride

Dialkyl aluminum hydride; and the like.

[171] The aluminum compound is more specifically, alkylaluminoxane and

A mixture of one or more selected from organic aluminum, most specifically methylaluminoxane, modified methylaluminoxane, tetraisobutylaluminoxane,

Trimethyl aluminum, triethyl aluminum, trioctyl aluminum, and

It may be one or a mixture of two or more selected from triisobutyl aluminum and the like.

On the other hand, the aluminum compound can serve as a scavenger to remove impurities that act as poisons to the reaction medium.

[173] According to an embodiment of the present invention, ethylene homopolymer or of ethylene and a-olefin

In the transition metal catalyst composition for preparing a copolymer, the preferred range of the ratio between the indene-based transition metal compound of the present invention and the catalyst activator, tetraarylborate compound, is the transition metal (M): boron atom (a molar ratio of 1: 0.1 to 100 Can be

[174] According to an embodiment of the present invention, ethylene homopolymer or ethylene and a-olefin

In the transition metal catalyst composition for preparing a copolymer, the preferred range of the ratio between the indene-based transition metal compound of the present invention and the cocatalyst aluminum compound is 1: 1 based on the molar ratio of the transition metal (M): aluminum atom (A1). It can be ~ 2,000 days.

[175] Specifically, in the transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and a-olefin according to an embodiment of the present invention, the indene-based transition metal compound, the tetraaryl borate compound and the aluminum compound of the present invention A preferred range of the ratio of liver is the molar ratio of the central metal (M): boron atom (B): aluminum atom (A1), and may be in the range of 1: 0.1-100: 1 to 2,000, preferably 1: 0.5-30: It may be in the range of 10 to 1,000, more preferably in the range of 1: 0.5-5: W 500.

[176] The indene-based transition metal compound and the tetraaryl borate compound of the present invention and

If the ratio between the aluminum compounds is out of the above range, the amount of cocatalyst is relatively small, so that the activation of the transition metal compound may not be fully accomplished, so that the catalyst activity of the indene-based transition metal compound may not be sufficient, or a cocatalyst more than necessary is used to produce it. The problem of a significant increase in cost can arise. It exhibits excellent catalytic activity for producing an ethylene homopolymer or a copolymer of ethylene and O _C -olefin within the above range, but within the above range depending on the purity of the reaction. 2020/174346 23 ?€1/162020/051519

The range of rates may vary.

[177] Another aspect of the present invention to achieve the above object is the above ethylene

It relates to a method for producing an ethylene homopolymer and an ethylene-based polymer selected from a copolymer of ethylene and (X-olefin) using a homopolymer or a transition metal group composition for preparing a copolymer of ethylene and (X-olefin).

[178] The method for producing an ethylene-based polymer using the ethylene homopolymer or a transition metal catalyst composition for producing a copolymer of ethylene and (X-olefin) is in the presence of an appropriate organic solvent, the indene-based transition metal catalyst, catalyst activator, Cocatalyst, and ethylene or

(This can be carried out by contacting the X-olefin comonomer. At this time, the indene-based transition metal catalyst, the catalyst activator, and the cocatalyst component, etc. can be separately introduced into the reactor, or each component can be mixed in advance and introduced into the reactor. Mixing conditions such as sequence, temperature, or concentration are not particularly limited. In addition, the catalyst activator may include a tetraaryl borate compound represented by Chemical Formula 1, and the cocatalyst is an aluminum compound and a boron compound described above. It may be one or a mixture of two or more selected from, etc.

[179] A method for producing an ethylene homopolymer or a copolymer of ethylene and an X-olefin according to an embodiment of the present invention is specifically, 幻

Tetraaryl borate compound and the tetraaryl borate compound

Injecting a catalyst activator composition containing the organic solvent used in the manufacturing step without separating; Injecting a single active point catalyst solution containing a non-Group 4 transition metal; Injecting the aluminum compound solution; And (1) Injecting ethylene; may include.

[180] As described above, the method for producing an ethylene homopolymer or a copolymer of ethylene and an X-olefin according to an embodiment of the present invention is in a state in which the tetraarylborate compound is dissolved in the organic solvent used in the manufacturing step Because it is injected into the furnace, it is advantageous for continuous solution processing, can solve the drawbacks of solid catalyst activators, and can avoid the use of aromatic hydrocarbon-based solvents such as toluene.

[181] The method for producing an ethylene homopolymer or a copolymer of ethylene and an X-olefin according to an embodiment of the present invention may further include the step of injecting this 01 -olefin.

[182] A preferred organic solvent that can be used in the above manufacturing method may be an aliphatic hydrocarbon-based solvent, and is hydrocarbon, and specific examples thereof include butane, isobutane, pentane, nucleic acid, heptane, octane, isooctane, nonane, decane, It may be one or two or more mixed solvents selected from linear aliphatic hydrocarbon-based solvents such as dodecane; and cyclic aliphatic hydrocarbon-based solvents such as cyclopentane, methylcyclopentane, cyclonucleic acid, and methylcyclonucleic acid.

[183] The organic solvent that can be used in the manufacturing method may be an aromatic hydrocarbon-based solvent.

[184] Specifically, when manufacturing an ethylene homopolymer, ethylene alone is used as a monomer. 2020/174346 24 ?€1/162020/051519

In this case, the suitable ethylene pressure is 1 to 1,000 atm, and more preferably 6 to 150 atm. In addition, the polymerization reaction temperature is between 25 °0 and 220 °0,

It is effective to be performed at 70 °0 to 220 °0 preferably, and more preferably 100 °0 to 220 °(:.

[185] In addition, when producing a copolymer of ethylene and (X-olefin, as a comonomer with ethylene, 03 to (: 18 olefin; 04 to 020 diolefin (I) 仙_£ &1); 05 20 cycloolefin or Clodiolefins; styrene and derivatives thereof; and the like. In addition, preferred examples of the (X-olefins of 03-08 above include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene , 1 -octene, 1 -decene, 1 -dodecene, 1 -hexadecene and 1 -octadecene, etc. Preferred examples of the 04^20 diolefin (D0 no & 1) are 1,3 -butadiene,

It may be selected from 1,4 -pentadiene and 2 -methyl-1,3-butadiene, and preferred examples of the 05^20 cycloolefin or cyclodiolefin include cyclopentene,

Cyclohexene, cyclopentadiene, cyclohexadiene, norbornene 0]¾0116116),

5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB) and

It can be selected from 5 -ethylidene- 2 -norbornene (ENB), etc. In the present invention, the above-described olefins can be single-polymerized or two or more kinds of olefins can be co-polymerized. In this case, the preferred ethylene pressure and polymerization reaction temperature are as described above. It may be the same as the case of manufacturing an ethylene homopolymer, and the ethylene-based copolymer manufactured according to the method of the present invention usually contains 30% by weight or more of ethylene, preferably 60% by weight or more, and more preferably 60 to 99% by weight. Included in the range of %.

[186] As described above, when the transition metal catalyst composition of the present invention is used, ethylene and

As a comonomer, it has a density of 3~(：10 (X-olefin is used appropriately and has a density of 0.85 /¥~0.960/¥, and 0.001~2,000 (3/4 of high-density polyethylene from an elastomer with a melting flow rate of ¾/min)) It can be manufactured easily and economically up to the domain.

[187] In addition, if the transition metal catalyst composition of the present invention is used, ethylene/propylene

It can be manufactured wonderfully, especially in an economical way, thanks to the easy injection of expensive diene.

01646-94, ^11 +4@ 125ᄋ It has a feature that makes it easy to manufacture EPDM products with (：) adjusted to 1 to 250, preferably 10 to 200.

[188] And the molecular weight when manufacturing an ethylene homopolymer or copolymer according to the present invention

Hydrogen can be used as a molecular weight control agent to control, usually 5,000 to

It has a weight average molecular weight (Mw) in the range of 1,000,000^0\.

[189] Since the transition metal catalyst composition presented in the present invention exists in a uniform form in the polymerization reactor, it is preferable to apply it to a solution polymerization process conducted at a temperature above the melting point of the polymer. However, U.S. Patent Nos. 4, 752, 597 As disclosed in the issue, the indene-based transition metal compound, catalyst activator, and co-catalyst are supported on a porous metal oxide support so that it can be used for slurry polymerization or gas phase polymerization as a non-uniform catalyst system. 2020/174346 25? 1/162020/051519

[19] The present invention is specifically described through the following examples, but the scope of the present invention is not limited by the following examples.

[191] Except where otherwise noted, all ligand and catalyst synthesis experiments are conducted under standard Schlenk under nitrogen atmosphere.

The organic solvent used in the reaction was refluxed under sodium metal and benzophenone to remove moisture and distilled immediately before use. The ¹ H-NMR analysis of the synthesized compound was conducted at room temperature (25). From ᄋ（：）

This was done using 500 MHz.

[192] Cyclonucleic acid, a polymerization solvent,

It was passed through and bubbled with high-purity nitrogen to sufficiently remove moisture, oxygen and other catalytic substances before use. The polymerized polymer was analyzed by the method described below.

[193] 1. Melt flow index (MI)

[194] It was measured according to ASTM 0 2839.

[195] 2. Density

[196] According to ASTM D 1505, it was measured using a density gradient tube.

[197] 3. 02 Analysis of conversion rate (%)

[198] The content ratio of unreacted ethylene and nitrogen as a standard material was measured using gas chromatography (（30）.

[199] 4. Molecular weight and molecular weight distribution

[200] Using the 11210 01^（：with Mixed-BX2+preC installed at 135°（：

It was measured in 1,2,3-trichlorobenzene solvent at a rate of 1.011止/111,

Molecular weight was calibrated using polystyrene standards.

[201] (Preparation Example 1) Preparation of Complex 1

[202] Preparation of compounds

[203]

1 -8

[204] (Production Example 1) Preparation of Complex 1

[205] Preparation of compound 1-k

[206]

2020/174346 26 ?€1/162020/051519

[207] In a nitrogen atmosphere, add Compound 1- 6.00 31.4 _01) to a 250 11 square bottom flask, and stir in anhydrous tetrahydrofuran (1¾印 150 11止).

-Butyl-1 -chloro-1 -methyl-1 -phenylsilaneamine (7.16 31.4 11111101)

After dissolving and adding tetrahydrofuran (1¾ seal (50 11止)), the mixture was stirred at room temperature for 12 hours. The solvent was removed by vacuum, and normal nucleic acid (150 1111 ᅴ) was added to dissolve it, and then dried celite 江_£ 1 The solids were removed with a filter filled with 如). All the solvent was removed to obtain 1 small of a viscous oil phosphorus compound (10.8 = 91.0%, diastereomer)

[208] ¹ H-NMR (500MH

0.156((1, 3¾, 0.703-0.830(111, 1¾, 0.976((1, 9¾, 1.501-1.528(111, 4¾, 3.089-3.217(111, 4¾, 3.501-3.604(111, 1¾, 5.259((1 , 1¾,

7.034-7.652 (111, 9¾.

[209] Preparation of Complex 1

[21 this

[211]

After dissolving Kee compound 1-1) (4.14 11.0 11111101) with diethyl ether (50 11 止)-78 ᄋ (: After reducing the furnace temperature, 1.5 M methyl lithium (29.4 11 止, 44.2 11111101) was slowly injected Raise the temperature to room temperature

Stir for 6 hours. The reaction was again cooled to -78° (:

A solution obtained by diluting tetrachlorotitanium (11 (No. ₄ ) (2.1 silver, 11.0 11111101) in anhydrous normal nucleic acid (30 1111 _^ )) was slowly added at −78° (:. After stirring at room temperature for 3 hours, the solvent was added to the solvent. It was removed by vacuum. After dissolving again in normal nucleic acid (100 11止), the solids were removed with a filter filled with dried celite ( _¥ 1 如). All the solvent was removed to obtain a red complex 1 (4.14 yield 83.2%; Diastereoisomer ratio ~ 1:3).

[212] ¹ H-NMR (500MHz, 0 ^ ₆ 1)111): 6 0.153((1, 3¾, 0.702-0.950(111, 6¾, 1.490)(1, 9¾, 2.951-3.442(111, 8¾, 5.360) ((1, 1¾, 6.698-7.89_, 9¾,

[213] (Example 1)

[214] Octadecyl-octadecylideneanilinium tetrakis (pentafluorophenyl)

Manufacture of borate [0 ₃₅ -C=N ÷(0 ₃₇ )(0 ₅頂₅ ) ₄ ]

[215] Etritil, round bottom flask in glove box

Tetrakis (pentafluorophenyl) borate 3 (3.25 11111101) was added. Then, 300 silver cyclonucleic acid was added to the round bottom flask and stirred at room temperature to prepare a yellow suspension. Dioctane as a solid in the suspended solution Decylaniline 1.95 (3.26_01) was added and stirred at room temperature for 30 minutes. The suspended solution became clear. 2020/174346 27 ?€1/162020/051519

If changed, it was used for the subsequent co-polymerization reaction without any further separation process.

[217] Copolymerization of 1-octene with ethylene by continuous solution process

[218] Using a continuous polymerization apparatus, co-polymerization of ethylene and 1-octene is carried out as follows:

As a single active point catalyst, the complex 1 synthesized in Preparation Example 1 was used, the solvent used was cyclonucleic acid, and the amount of catalyst used was as described in Table 1 below. The input amount of II is the amount of complex 1 synthesized in Preparation Example 1, the amount of new input is the amount of triisobutylaluminum, and the amount of the catalyst activator is octadecyl octadecylideneanilinium synthesized in Example!

The amount of tetrakis (pentafluorophenyl) borate added is indicated respectively. Complex 1 was dissolved in cyclonucleic acid at a concentration of 0.3 and injected, and triisobutylaluminum was added to cyclonucleic acid with 3! _^ Injected at a concentration of octadecyl-N-octadecylideneanilinium tetrakis (pentafluorophenyl) borate to cyclonucleic acid

It was dissolved at a concentration and injected, and synthesis was carried out using 1-octene as a comonomer.

The 02 conversion rate of the reactor can be estimated through the reaction conditions and the temperature gradient in the reactor when polymerization into one polymer under each reaction condition. The molecular weight was controlled as a function of the reactor temperature and 1-octene content, and the conditions are shown in Table 1 below. The results are described.

[219] （Comparative Example 1）

[22] Copolymerization of ethylene and 1-octene by continuous solution process

[221] Using a continuous polymerization apparatus, the co-polymerization of ethylene and 1-octene is carried out as follows.

Complex 1 synthesized in Preparation Example 1 was used as a single active point catalyst, and cyclonucleic acid was used as the solvent, and the catalyst used is as described in Table 1 below. II input amount is the input amount of the complex 1 synthesized in Preparation Example 1 above, the new input amount is the input amount of triisobutyl aluminum, the input amount of the catalyst activator

The amount of trityltetrakis (pentafluorophenyl) borate (1 l) is indicated, respectively. Complex 1 was dissolved in toluene at a concentration of 0.1 and injected, and triisobutylaluminum and was added to the concentration of toluene by the composition of Table 1 below. It was prepared and injected, and synthesis was carried out using 1-octene as a comonomer. The 02 conversion rate of the reactor can be estimated through the reaction conditions and the temperature gradient in the reactor when polymerization into one polymer under each reaction condition. The molecular weight was controlled as a function of the reactor temperature and 1-octene content, and the conditions are shown in Table 1 below. The results are described.

[222] 2020/174346 28 ?€1/162020/051519

[Table 1]

[223] As shown in Table 1 above, Example 2, which was polymerized using the catalyst composition according to the present invention, exhibited a high conversion rate of ethylene even under high temperature (180 or more) conditions, and low density and high molecular weight. It was confirmed that a high molecular weight ethylene-based copolymer having an MI value could be easily prepared. In addition, Example 2 showed the same level of ethylene conversion even with a small amount of catalyst compared to Comparative Example 1. It was confirmed that the catalyst composition according to the invention exerts an excellent effect on the activation of a single active point catalyst.

[224] In particular, the new tetraarylborate compound according to the present invention is soluble in aliphatic hydrocarbon-based solvents such as cyclonucleic acid, not aromatic hydrocarbon-based solvents, depending on the selection of the cations of the alkylideneanilinium structure. Such solubility For this reason, the transition metal catalyst composition according to the present invention provides a solution-type catalyst activator containing an aliphatic hydrocarbon-based solution to facilitate the operation of commercial processes and can be a means of solving the disadvantages of the solid catalyst activator. have. 2020/174346 29 ?€1/162020/051519

[225] As seen above, the embodiments of the present invention have been described in detail, but those who have ordinary knowledge in the technical field to which the present invention belongs, do not depart from the spirit and scope of the present invention defined in the appended claims. It will be possible to implement this invention in various ways without changing it.

Claims

2020/174346 30 1^(:1^2020/051519 Claims [Claim 1] Tetraarylborate compounds represented by the following Chemical Formula 1:

[Chemical Formula 1] Three to four

V

In Formula 1 above,

8 is a boron atom;

Four ¹ is (06 30) aryl, and the aryl of the above ¹ is ((：1 30) alkyl,

May be further substituted with one or more substituents selected from halo(0 30) alkyl and 6 30) aryl(0 30) alkyl;

4 ² is fluorine-substituted 6 30) aryl;

¹ is hydrogen or (0 30) alkyl;

II ² is (0 30) alkyl, or may be linked to II ¹ to form a ring, and the ring is (0 30) alkyl, ((: 1 30) alkoxy, halo (0 30) alkyl,

3 30) Cycloalkyl, (（：1 30）alkyl 6 30）aryl, 6 30）aryl, （6 30）aryloxy ,（（：1 30）alkyl（ 6 30）aryloxy,

（6 30）aryl（（：1 30）alkyl and

It may be further substituted with one or more substituents selected from ((0 30)alkyl(6 30)aryl)(0 30)alkyl.

[Claim 2] In paragraph 1,

Tetraaryl borate compound represented by the following formula 2:

[Formula 2]

In Formula 2,

II ¹ and ² are the same as the definition in Formula 1 of claim 1;

II ¹¹ to II ¹⁵ are each independently hydrogen, ((：1 30) alkyl, halo(0 30) alkyl or (6 30) aryl((：1 30) alkyl.

[Claim 3] In paragraph 1,

Tetraaryl borate compound represented by the following formula 3:

[Formula 3] 2020/174346 31 ?€1/162020/051519

In Formula 3 above,

Above: 8 is the same as the definition in formula 1 in claim 1;

II ¹¹ to II ¹⁵ are each independently hydrogen, ((:1 30) alkyl, halo(0 30) alkyl, or (6 30) aryl((:1 30) alkyl;

II is an integer selected from 2 to 6;

II ²¹ and II ²² are each independently hydrogen, ((：1 30) alkyl, (0 30) alkoxy, halo(0 30) alkyl, 3 30) cycloalkyl, (0 30) alkyl 6 30) aryl, 6 30) Aryl, 片 6 30) Aryloxy, (0 30) Alkyl (06 30) Aryloxy, (6 30) Aryl (0 30) Alkyl or

（（（：1 30）alkyl（06-030）aryl）（（：1 30）alkyl.

[Claim 4] In paragraph 1,

Above II ¹ and! At least one selected from I ² is (8 30) alkyl, a tetraarylborate compound.

[Claim 5] In paragraph 1,

II ¹ and II ² are each independently (02-030) alkyl, a tetraarylborate compound.

[Claim 6] The tetraaryl borate compound according to any one of claims 1 to 5;

A single active point catalyst containing a group 4 transition metal; And

Aluminum compounds;

Transition metal catalyst composition for producing an ethylene homopolymer or a copolymer of ethylene and (X-olefin containing).

[Claim 7] In paragraph 7,

The transition metal catalyst composition,

The ethylene homopolymer or ethylene and containing the organic solvent used in the production step of the tetraarylborate compound without separating

«-Transition metal catalyst composition for manufacturing copolymers of olefins.

[Claim 8] In paragraph 6,

The single active point catalyst,

Metallocene catalyst, ethylene homopolymer or ethylene and (X-olefin

Transition metal catalyst composition for manufacturing copolymers.

[Claim 9] In paragraph 6,

The single active point catalyst,

Transition metal catalyst composition for manufacturing ethylene homopolymer or copolymer of ethylene (X-olefin), which is an indene-based transition metal compound represented by the following chemical formula: 2020/174346 32 ?€1/162020/051519

[Formula City

It is Neil, and II _! £]alkyl or alkenyl may be further substituted with one or more substituents selected from halogen, 6 30) aryl and (0 30) alkyl 6 30) aryl;

4 片6 30）Aryl, and the above _! £]aryl is (0 30) alkyl,

May be further substituted with one or more substituents selected from halo(0 30) alkyl and 6 30) aryl(0 30) alkyl;

II ₂ to II ₅ are each independently hydrogen, (0 30) alkyl, (0 30) alkoxy, halo (0 30) alkyl, 3 20) cycloalkyl, (0 30) alkyl (6 30) aryl, 6 30 ）Aryl, 6 30) aryloxy, (0 30) alkyl (06 30) aryloxy, (6 30) aryl (0 30) alkyl or

（（0^30）alkyl（6 30）aryl）（0 30）alkyl, or can form a fused ring by linking with an adjacent substituent from 11 ₂ to above, and the fusion ring is （0 30）alkyl, 1 30) alkoxy, halo (0 30) alkyl, (3 20) cycloalkyl, (() 1 30) alkyl (6 30) aryl, (06 30) aryl, (06 30) aryloxy,

One or more substituents selected from （（：1 30）alkyl（ 6 30）aryloxy,（ 6 30）aryl（（：1 30）alkyl and （（0 30）alkyl（ 6 30）aryl）（0 30）alkyl Loader can be replaced;

₉ is (0 30) alkyl, 3 20) cycloalkyl or

(06-030) is aryl ((: 1 30) alkyl;

11 ₆ and 11 ₇ are each independently (0 30) alkyl, halo (0 30) alkyl,

(0020) Cycloalkyl, (6 30) aryl, ((1 30) alkyl (06 30) aryl, ((:1 30) alkoxy(6 30) aryl or (6 30) aryl ((:1 30) alkyl Or, the II ₆ and II ₇ may be linked to each other to form a ring, the ring is (0 30) alkyl, halo ((: 1 30) alkyl, (6 30) aryl (0 30) alkyl,

(0 30) alkoxy, (3 20) cycloalkyl, (6 20) aryl,

May be further substituted with one or more substituents selected from ((:1 30) alkyl(6 30) aryl and (6 20) aryloxy;

Element ₈ is hydrogen or (0 30) alkyl; 2020/174346 33 ?€1/162020/051519

X _! And ₂ are each independently halogen, (0 30) alkyl, (02^20) alkenyl, 3 20) cycloalkyl, (6 30) aryl, (06 30) aryl ((1 30) alkyl,

（（（：1 30）alkyl（06 30）aryl）（0 30）alkyl,（（：1 30）alkoxy,

（6 30）aryloxy ,（（：1 30）alkyl（ 6 30）aryloxy,

（（：1 30）alkoxy片6 30）aryloxy, -（샜溫 ¾ ¾。, yo yo ¾ ^中 ¾ ¹¹ or (（：1 30) alkylidene;

The II to II lines are independently (0 30) alkyl, (06 20) aryl,

(6 20) aryl ((1 30) alkyl, ((30) alkyl (6 20) aryl or (0020) cycloalkyl;

II ⁶ to II are each independently (0 30) alkyl, (06 20) aryl,

（06-020）aryl（（： 1 30）alkyl,（（： 1 30）alkyl（06-020）aryl,

（3 20）cycloalkyl, tri（（：1 30）alkylsilyl or

Tri(06-020)arylsilyl;

However, if one of X _I or ₂ is (0 30) alkylidene, the other is ignored.

[Claim 10] In paragraph 6,

The aluminum compound,

As a mixture of one or more selected from alkylaluminoxane and organic aluminum, methylaluminoxane, modified methylaluminoxane,

Transition metal catalyst composition for producing ethylene homopolymer or a copolymer of ethylene and (X-olefin), which is a mixture of one or two or more selected from tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[Claim 11] In paragraph 6,

The ratio of the single active point catalyst to the tetraarylborate compound is a transition metal (M): boron atom (a molar ratio of blood, in the range of 1: 0.1 to 100, a transition metal for manufacturing an ethylene homopolymer or a copolymer of ethylene and an X-olefin) Catalyst composition.

[Claim 12] In paragraph 6,

The ratio of the single active point catalyst, the tetraarylborate compound and the aluminum compound,

Transition metal (: boron atom (P: aluminum atom (new)) molar ratio, in the range of 1: 0.1-100: 1 to 2,000, a transition metal catalyst composition for the production of an ethylene homopolymer or a copolymer of ethylene and (X-olefin).

[Claim 13] In paragraph 12,

The ratio of the single active point catalyst, the tetraarylborate compound and the aluminum compound,

Transition metal (M): boron atom (P: aluminum atom (show 1) molar ratio of 1: 0.5 to 5: 2020/174346 34 ?€1/162020/051519

A transition metal catalyst composition for producing an ethylene homopolymer or a copolymer of ethylene and (X-olefin) in the range of ^ to 500.

[Claim 14] A method for producing an ethylene homopolymer or a copolymer of ethylene and (X-olefin) using the transition metal catalyst composition according to paragraph 6.

[Claim 15] In paragraph B,

The (X-olefin is,

Propylene, 1 -butene, 1 -pentene, 1 -hexene, 1 -heptene, 1 -octene, 1 -decene, 1 -undecene,

1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -aitocene, 3 -butadiene,

1,4-pentadiene and 2-methyl-1,3-butadiene is a mixture of one or two or more selected from, the ethylene and _(the ethylene content in the copolymer of X-olefin is 30 to 99% by weight, ethylene homopolymer or Method for producing a copolymer of ethylene and (X-olefin.

[Claim 16] The method of claim 15,

As a comonomer polymerized with the ethylene,

Cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbornene,

5 -vinylidene- 2 -norbornene, 5 -methylene -2 -norbornene, 5 -ethylidene-2 -norbornene and ethylene and ethylene homopolymer or ethylene, further comprising one or more mixtures selected from styrene. (Method for producing a copolymer of X-olefin.

[Claim 17] In paragraph B,

The pressure in the ethylene monopolymerization or co-polymerization reactor of ethylene and (X-olefin is 6 to 150 atm, and the polymerization reaction temperature is 50 to 200 ᄋ (: Phosphorus, ethylene homopolymer or a method for producing a copolymer of ethylene and (X-olefin) .

[Claim 18] Injecting the tetraaryl borate compound according to any one of claims 1 to 5 and a group activating composition comprising the organic solvent used in the preparation step of the tetraaryl borate compound without separating;

Injecting a single active point catalyst solution containing a group 4 transition metal; Injecting an aluminum compound solution; And

Injecting ethylene; a method for producing an ethylene homopolymer or a copolymer of ethylene and «-olefin, including.

[Claim 19] In paragraph 18,

(The method of producing an ethylene homopolymer or a copolymer of ethylene and (X-olefin) further comprising the step of injecting an X-olefin.