WO2016204469A1

WO2016204469A1 - Method for producing metallocene-supported catalyst

Info

Publication number: WO2016204469A1
Application number: PCT/KR2016/006264
Authority: WO
Inventors: 유영석; 조경진; 권혁주; 최이영; 이기수; 송은경; 김우리
Original assignee: 주식회사 엘지화학
Priority date: 2015-06-15
Filing date: 2016-06-13
Publication date: 2016-12-22

Abstract

The present invention relates to a method for producing a metallocene-supported catalyst, capable of more effectively preparing a polyolefin, which has a molecular weight distribution for good swelling, through increased polymer elasticity, and thus can preferably be used for blow molding or the like.

Description

【Specification】

[Name of invention]

Method for preparing metallocene supported catalyst

Technical Field

Cross Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0084483 J: June 15, 2015 and Korean Patent Application No. 10-2016-0029835 filed March 11, 2016, and the Korean Patent Application All content disclosed in these references is included as part of this specification.

The present invention relates to a method for preparing a metallocene supported catalyst which can more effectively prepare polyolefins which can be preferably used for blow molding, as the polymer elasticity increases and the swell (swel l) has a molecular weight distribution. will be. Background Art

In general, for products manufactured using blow molding, excellent workability, mechanical properties and stress cracking resistance are required. Therefore, there has been a continuous demand for a technique for producing a polyolefin which can be suitably used for blow molding and the like by satisfying a large molecular weight, a wider polymodal molecular weight distribution, a uniform comonomer distribution, and the like.

On the other hand, metallocene catalysts using Group 4 transition metals are easier to control the molecular weight and molecular weight distribution of polyolefins than conventional Ziegler-Natta catalysts, and can control the comonomer distribution of polymers, resulting in improved mechanical properties and processability. And so on. However, polyolefins prepared using metallocene catalysts have a problem of poor workability due to narrow molecular weight distribution.

In general, the wider the molecular weight distribution, the higher the viscosity decrease according to the shear rate, and thus the excellent workability in the processing area.Polylefin made of a metallocene catalyst has a high shear rate due to the relatively narrow molecular weight distribution. High viscosity, so it takes a lot of load or pressure during extrusion Extrusion productivity is lowered, bubble stability is greatly reduced during blow molding processing, and the surface of the manufactured blow molded molded article is uneven, resulting in a decrease in transparency.

In addition, the conventional ethylene polymerization has participated in the polymerization by using a complex of titanocene (Tebno reagent) and alkylaluminum (Alkylaluminium) called Tebbe reagent and has played a role in increasing the molecular weight. The main characteristic of the Tebbe reagent is that the Tebbe reagent is activated by a base to form titaniumalkyl idene, which is related to the double bond. , Metathesis, etc.), but the role of Tebe reagents in ethylene polymerization without the addition of lewis bases is not known. In 1990, the Petasis group succeeded in ring-closing metathesis by simply adding heat to Tebe reagents. Accordingly, it is presumed that Tebbe reagent forms titaniumalkyl idene by polymerization temperature when it participates in polymerization, resulting in polymerization using alkylidene-specific reactions.

Accordingly, as the polymer elasticity increases and the molecular weight distribution improves the swell, the technology and development can be more effectively produced the polyolefin which can satisfy mechanical properties and processability at the same time and can be preferably used for blow molding. This is constantly required.

[Content of invention]

[Problem to solve]

Accordingly, the present invention provides a method for preparing a metallocene-supported catalyst which can more effectively prepare a polyolefin which can be preferably used for blow molding, as the polymer elasticity increases and the molecular weight distribution of the swell is improved. will be.

In addition, the present invention is prepared in the presence of a metallocene supported catalyst prepared from the production method, it can satisfy mechanical properties and processability at the same time To provide a polyolefin which can be preferably used for blow molding. ^'

[Measures of problem]

The present invention is to prepare a molecular weight regulator composition by mixing a cyclopentadienyl metal compound of Formula 1 and an organoaluminum compound of Formula 2 for 50 to 108 hours at room temperature; And supporting at least one metallocene compound represented by one of the following Chemical Formulas 3 to 6 and the molecular weight modifier composition on a carrier; and a supported metallocene catalyst.

In Formula 1, Cp ¹ and Cp ² are each independently a ligand including a cyclopentadienyl group, an indenyl group, or a fluorenyl group; R ¹ and R ² are each independently a substituent of Cp ¹ and Cp ² , hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms, Aryl having 6 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, heteroalkenyl having 2 to 20 carbon atoms, heteroalkylaryl having 6 to 20 carbon atoms, heteroarylaryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms, ; M ¹ is a Group 4 transition metal element; X is halogen,

[Formula 2]

R ³ R ⁴ R ⁵ A1

R ³ , R ⁴ and R ⁵ in Formula 2 are each independently an alkyl group having 4 to 20 carbon atoms or halogen, at least one of R ³ , R ⁴ and R ⁵ is an alkyl group having 4 to 20 carbon atoms,

[Formula 3]

(Cp ⁵ R ^a ) n (Cp ⁶ R ^b ) M ¹ Z ¹ ₃ -n

In Chemical Formula 3,

M ¹ is a Group 4 transition metal;

Cp ⁵ and Cp ⁶ are the same as or different from each other, and each independently Cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, and any one selected from the group consisting of hydrocarbons having 1 to 20 carbon atoms, ;

R ^a and R ^b are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 Alkenyl to C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;

Z ¹ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

n is 1 or 0;

[Formula 4]

(Cp ⁷ R ^c ) _m B ¹ (Cp ⁸ R ^d ) M ² Z ² ₃ - _m

In Chemical Formula 4,

M ² is a Group 4 transition metal;

Cp ⁷ and Cp ⁸ 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 a hydrocarbon having 1 to 20 carbon atoms;

R ^c and R ^d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 C20 to C40 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ² is a halogen atom, C1 ^' to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkyl Liden, substituted or unsubstituted Amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

B ¹ is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp¾ ^c ring with the Cp ⁴ R ^d ring or crosslinks one Cp ⁴ R ^d ring with M ² or Is a combination of;

m is 1 or 0;

[Formula 5] ^'

(Cp ⁹ R ^e ) B ² (J) M ³ Z ³ ₂ ^'

In Chemical Formula 5,

M ³ is a Group 4 transition metal;

Cp ⁹ is 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 Can be;

R ^e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl C7-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkynyl;

Z ³ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

B ² ^' is one or more or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp ⁵ R ^e ring and J;

J is any one selected from the group consisting of NR ^f , 0, PR ^f and S, wherein R ^f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl, [Formula 6]

In Chemical Formula 6,

A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 C20 alkoxyalkyl group, C3 to C20 heterocycloalkyl group, or C5 to C20 heteroaryl group;

D is — 0—, -S-, -N (R)-or -SKRKR ')-, wherein R and R' are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group of C1 to C20, C2 To C20 alkenyl group, or C6 to C20 aryl group;

L is a C1 to C10 straight or branched chain alkylene group;

B is carbon, silicon or germanium;

Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;

M is a Group 4 transition metal;

X ¹ and X ² are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

C ¹ and C ² are the same as or different from each other, and each independently

7a, 7b, or 7c represented by one of the following formulae, except that C ¹ and C ² are all of the formula 7c;

[Formula 7a]

[Formula 7c]

In Formulas 7a, 7b, and 7c, R1 to R17 and R1 'to R9' are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkyl Silyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, Two or more adjacent to each other of R10 to R17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring. The present invention also provides a method for producing a polyolefin, which comprises polymerizing an olefin monomer in the presence of a metallocene supported catalyst. The present invention also provides a polyolefin produced according to the above production method. Hereinafter, a method for preparing a metallocene supported catalyst, a metallocene supported catalyst prepared therefrom, a method for preparing polyolefin using the same, and a polyolefin prepared therefrom will be described.

According to one embodiment of the invention, a metallocene supported catalyst is prepared by supporting a specific molecular weight modifier composition with a metallocene compound on a carrier. The method for preparing the metallocene supported catalyst may include mixing a cyclopentadienyl metal compound of Formula 1 and an organoaluminum compound of Formula 2 to stir at room temperature for 50 to 108 hours to prepare a molecular weight modifier composition; And supporting at least one metallocene compound represented by one of Chemical Formulas 3 to 6 and the molecular weight modifier composition on a carrier.

[Formula 3]

In Chemical Formula 3,

M ¹ is a Group 4 transition metal;

Cp ⁵ and Cp ⁶ are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, intenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;

Z ¹ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

n is 1 or 0;

[Formula 4] In Chemical Formula 4,

M ² is a Group 4 transition metal;

Cp ⁷ and Cp ⁸ 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 a hydrocarbon having 1 to 20 carbon atoms;

Z ² is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

m is 1 or 0;

[Formula 5]

(Cp ⁹ R ^e ) B ² (J) M ³ Z ³ ₂

In Chemical Formula 5,

M ³ is a Group 4 transition metal;

Cp ⁹ is any one selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, 7-tetrahydro-1-indenyl and fluorenyl radicals, which are substituted with hydrocarbons having 1 to 20 carbon atoms Can be;

R ^e is hydrogen, alkyl of C1 to C20, alkoxy of C1 to C10, alkoxyalkyl of C2 to C20, aryl of C6 to C20, aryloxy of C6 to C10, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

B ² is at least one or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp¾ ^e ring and J;

J is any one selected from the group consisting of NR ^f , 0, PR ^f and S, wherein R ^f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl,

[

In Chemical Formula 6,

A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group

C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 alkoxyalkyl group, C3 to C20 heterocycloalkyl group, or C5 to C20 hetero Aryl group;

D is -0-, -S-, -N (R)-or -Si (R) (R ') _, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, C1 to An alkyl group of C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20;

L is a C1 to C10 straight or branched chain alkylene group;

B is carbon, silicon or germanium;

Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20

C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;

M is a Group 4 transition metal; X ¹ and X ² are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

C ¹ and C ² are the same as or different from each other, and are each independently represented by one of the following Formulas 7a, 7b, or 7c, except that C ¹ and C ² are both Formula 7c;

[

[

In Chemical Formulas 7a, 7b, and 7c, R1 to R17 and R1 'to R9' are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 Alkylsilyl group, C1 to C20 and silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, two or more adjacent to each other of R10 to R17 are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring. In Formula 1, Cp ¹ and Cp ² are each independently a ligand including a cyclopentadienyl group, indenyl group, or fluorenyl group; R ¹ and R ² are each independently a substituent of Cp ¹ and Cp ² , hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms, Aryl having 6 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, heteroalkenyl having 2 to 20 carbon atoms, heteroalkylaryl having 6 to 20 carbon atoms, heteroarylaryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms, ; M ¹ is a Group 4 transition metal element; X is halogen. In particular, R ¹ and R ² may be each independently selected from the group consisting of hydrogen, methyl, ethyl, butyl, and t-butoxy nucleus. In addition, M ¹ is a Group 4 transition metal element, preferably may be selected from the group consisting of titanium, zirconium and hafnium. In addition, X is a halogen, preferably may be selected from the group consisting of F, (: 1, Br and I.

[Formula 2]

R ³ R ⁴ R ⁵ A1

R ³ , R ⁴ and R ⁵ in Formula 2 are each independently an alkyl group having 4 to 20 carbon atoms or a halogen, and at least one of R ³ , R ⁴ and R ⁵ is an alkyl group having 4 to 20 carbon atoms. In particular, R ³ , R ⁴ and R ⁵ may each independently be an isobutyl group.

As a result of the experiments of the present inventors, it was confirmed that the use of a metallocene catalyst including a specific molecular weight modifier composition directly mixed with a catalyst precursor enables the production of polyolefins having a larger molecular weight and a wider molecular weight distribution with improved activity. The mechanism of action of these molecular weight regulators has not been elucidated. However, when these specific molecular weight regulators are mixed with catalyst precursors, the ear ly-t rans it on The metal alkyl idenes made from metals have different partial charges between the metals and the alkyl groups, so that the alkyl idenes with partial negative charges are combined with the met l locenes of the forward transition metals with l ewi s acidic c than aluminum alkyls. It is expected to increase the molecular weight while having intermediates in the form and to enable the production of polyolefins having large molecular weights and wider distributions.

According to one specific embodiment of the present invention, a metallocene supported catalyst may be prepared by reacting a specific molecular weight modifier composition with a metallocene compound as described above as described in Scheme 1 and supported on a carrier.

^''

Helero (Homo | dfniicleaf catalyst catalyst-in particular, in the present invention, extends the meaning of molecular weight control action by the hydrogen reactivity change of the existing Tebbe type reagent, the precursor and titanocene (Ti tanocene) This technique is used to control the molecular weight by directing the reaction and controlling the reaction of hydrogen by using a small amount of Ti tanocene. This results in instability, ie, the use of a minimum molecular weight modifier to enable efficient molecular weight control.

In the production method of this embodiment, the molecular weight regulator composition is 0.1 to 1.0 equivalent (eq.), Preferably 0.1 to 1 to the cyclopentadienyl metal compound of Formula 1 and the organoaluminum compound of Formula 2 Mixing in 0.5 equivalents, it can be produced by stirring at room temperature, for example 50 to 108 hours, preferably 62 to 90 hours at 22.5 to 25 I. The molecular weight modifier composition is a mixture of the cyclopentadienyl metal compound of Formula 1 and the organoaluminum compound of Formula 2, or a reaction product thereof, for example, formed by reacting a compound of Formula 1 and Formula 2 Organometallic complexes.

In addition, the molecular weight regulator including a specific substituent in the cyclopentadienyl group of the formula (1) and the organic functional group of the formula (2) shows a significantly improved solubility compared to the conventional, uniformly catalyst with excellent precursor properties (homogenei ty) with the catalyst precursor The composition can be formed to exhibit excellent polymerization performance.

According to one embodiment, the metallocene supported catalyst of the present invention has a molecular weight distribution in which the swell (swel l) is improved by increasing the molecular weight and polymer elasticity, it can exhibit excellent mechanical properties and processability, blow The polyolefin which can be preferably used for molding etc. can be manufactured more effectively.

The molecular weight modifier generated by reacting the cyclopentadienyl metal compound of Formula 1 and the organoaluminum compound of Formula 2 may be represented by the following Formula 8, Formula 9, Formula 10, or Formula 11.

On the other hand, when using titanocene alone in a conventional manner, polymer polymerization is almost It does not occur and the tebbe type reagent also does not participate in the polymer polymerization. Organo lithium and organo magnesium have a mechanism that acts as a strong base that has nothing to do with ti tanocene carbine. The present invention focuses on the chemical reaction that Ti tanocene combined with organoaluminum can be formed by thermal decomposition of Ti tanium carbene, which can result from the carbene, and is most important in the formation of polymers. By more aggressively reacting the metallocene precursor that plays a role, there is an advantage that the maximum molecular weight control effect can be obtained by using a minimum titanocene (ti tanocene). In one embodiment, the molecular weight modifier composition includes the compounds of Formulas 1 and 2 in the form of a mixture that does not react with each other, or a reaction product of the compounds of Formulas 1 and 2, for example, a metal of these compounds. The elements may be included in the form of organometallic complexes in which X and / or R ¹ , R ² and R ³ are bonded to each other. In this case, together with the organometallic complex, some of the unreacted compounds of Formula 1 and / or Formula 2 may further be included.

As already mentioned above, the molecular weight modifier assists the activity of the metallocene catalyst, allowing polymerization to proceed with great activity even in the presence of a relatively small amount of metallocene catalyst, Increased elasticity allows the production of polyolefins having a molecular weight distribution with better swels.

In the molecular weight modifier composition, specific examples of the cyclopentadienyl metal compound of Formula 3 include biscyclopentadienyl titanium dichloride, biscyclopentadienyl zirconium dichloride, biscyclopentadienyl hafnium dichloride, and bis indenyl. Titanium dichloride or bisflorenyltitanium dichloride, bis (2-ethylcyclopenta-2, 4-diene-1-yl) titanium dichloride, bis (2-butylcyclopenta-2, 4-diene-1-yl Titanium dichloride, bis (2- (6-t-subsidiary-nuclear) cyclopenta-2, 3-diene-1-yl) titanium dichloride, bis (2-ethylcyclopenta-2, 4-diene- 1-day) zirconium Dichloride, bis (2-ethylcyclopenta-2, 4-dieen-1-yl) hafnium dichloride, and the like. In addition, specific examples of the organoaluminum compound of Formula 4 include triisobutyl aluminum, trinuclear aluminum, trioctyl aluminum, diisobutyl aluminum chloride, dinuxyl aluminum chloride, isobutyl aluminum dichloride, and the like.

In addition, the compound of Formula 1 and the compound of Formula 2 are each a metal element (M) contained in the formula (3), aluminum (A1) contained in the formula (4) as a molar ratio, about 1: 0.01 to 1: 100 Or in a molar ratio of about 1: 0.5 to 1: 10.

The molecular weight modifier may be used in an amount of about 0.01 to 10 parts by weight, or about 0.01 to 1 part by weight based on 100 parts by weight of the catalyst precursor. In addition, the molecular weight modifier is about 1 to 85 mol, preferably about 3 to 70 mol, more preferably about 5 to 55 mol%, black 10 to 50 mol% based on the total amount of the catalyst precursor Can be used. As it is used in this content range, the effect and effect of the addition of the molecular weight modifier are optimized, and the polymer melt index is low, the molecular weight distribution is wide, the molecular weight is large, and the stress cracking resistance is improved more than the density or polymer melt index. Polyolefin can be obtained. In particular, when an excessive amount of organoaluminum is present in the reaction vessel, it reacts with the metallocene catalyst as in general alkylaluminum, causing deactivation while causing deactivation. Accordingly, the present invention has the advantage of not inhibiting the activity of the existing metallocene precursor itself by reacting the catalytic amount of the molecular weight regulator with the maximum efficiency compared to the precursor. In addition, the present invention can effectively control the molecular weight of a single or common supported catalyst while using a small amount of the molecular weight regulator corresponding to the amount of catalyst of the metallocene precursor supported when preparing the metallocene supported catalyst. Existing conventional techniques have been shown to simply increase the molecular weight, but the present invention has the advantage of finely adjusting the polymer structure according to the amount of the molecular weight regulator while maintaining the polymerization conditions without activity degradation. In addition, there is no supported heterogeneity itself due to interaction instability with the cocatalyst according to the precursor, for example, MA0, in the preparation of the supported catalyst, thereby providing a supported catalyst having excellent catalyst stability. Can be. On the other hand, in the production method of the embodiment, the metallocene supported catalyst is to be used in the form of a supported catalyst in which the metallocene compound and the molecular weight modifier composition is supported on a carrier. In addition, the metallocene catalyst may be used together by common hybridization of two different subphase metallocene compounds, or may include only one metallocene compound.

The metallocene compound represented by Chemical Formula 3 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

In addition, the compound represented by Chemical Formula 4 may be, for example, a compound represented by the following structural formula, but is limited thereto.

In addition, the compound represented by Formula 5 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

In Formula 6, Group 4 transition metal (M) may include titanium, zirconium, hafnium, and the like, but is not limited thereto.

In the metallocene compound of Chemical Formula 6, R1 to R17 and R1 to R9 of Chemical Formulas 7a, 7b, and 7c are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nucleosil group, heptyl group, octyl group, phenyl group, halogen group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, It is more preferable that it is a trimethylsilyl methyl group, a meso group, or an ethoxy group, but it is not limited only to this.

In the metallocene compound of Chemical Formula 6, L is more preferably a C4 to C8 linear or branched alkylene group, but is not limited thereto. In addition, the alkylene group may be unsubstituted or substituted with an alkyl group of C1 to C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20.

In the metallocene compound of Chemical Formula 6, A is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert-subspecific methyl group, 1-specific It is preferably an ethyl group, 1-methyl-1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group, but is not limited thereto. In addition, B is preferably silicon, but is not limited thereto.

The metallocene compound of Formula 6 may be a non-covalent electron pair which forms a structure in which an indeno indol derivative and / or a fluorene derivative are crosslinked by a bridge, and may act as a Lewis base to the ligand structure. By having the Lewis acid property of the carrier, it has a high polymerization activity even when supported on the surface. In addition, due to the electronically rich indeno indole and / or fluorene group, the activity is high, and due to the proper steric hindrance and the electronic effect of the ligand, the reaction is not only low but also maintains high activity even in the presence of hydrogen. . In addition, the beta-hydrogen of the polymer chain in which the nitrogen atom of the intenoindole derivative is grown is stabilized by hydrogen bonding, thereby inhibiting the beta-hydrogen el itninat ion, thereby adding an ultra high molecular weight olefin polymer.

According to an embodiment of the present invention, a specific example of the structure represented by Chemical Formula 7a may include a structure represented by one of the following structural formulas, but is not limited thereto.

Further, specific examples of the structure represented by Chemical Formula 7b may include a structure represented by one of the following structural formulas, but is not limited thereto.

In addition, specific examples of the structure represented by Chemical Formula 7c may include a structure represented by one of the following structural formulas, but is not limited thereto.

In addition, specific examples of the metallocene compound represented by Chemical Formula 6 may include a compound represented by one of the following structural formulas, but only

? 9Ζ900 / 9ΐΟΖΗΜ / Χ3 <Ι 69 »0Ζ / 9ΐ0Ζ OAV

It can be obtained by performing metallization (metal l at i on) by adding a metal precursor compound, but is not limited thereto.

In the production method of the above embodiment, the metallocene compound and the molecular weight modifier composition as described above are used in the form of a supported catalyst supported on a carrier. The supporting step may be performed by mixing the carrier, the metallocene catalyst and the molecular weight modifier composition ^{at a} temperature of 30 to 100 ^° C., preferably 35 to 90 t, or 40 to 80 ^° C. at 1 hr to 12 hr, Preferably it can be carried out by stirring for 1 hr to 4 hr.

Meanwhile, the metallocene supported catalyst may be in the form of a supported metallocene catalyst in which a metallocene compound and a promoter are supported on a carrier. According to an example, two or more different metallocene compounds and a promoter may be different from each other. It may be a common supported metallocene catalyst comprising a.

In this case, the carrier may be silica, silica-alumina, silica-magnesia, or the like, and may be any carrier known to support other metallocene catalysts. In addition, such a carrier may be used in a dry state at a high temperature, the drying temperature may be, for example, about 180 to 800 ^° C. If the drying temperature is too low, excess separation on the carrier may react with the promoter to degrade the performance. If the drying temperature is too high, the hydroxyl group content is too low on the surface of the carrier to reduce the reaction space with the promoter. can do.

In particular, the carrier may be one carrying an aluminum-containing first cocatalyst of the formula (12).

[Formula 12]

[Al (R ¹⁸ ) -0-] _n -In formula (12), R ¹⁸ is each independently a halogen, a halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, n is an integer of 2 or more. In the present invention, the molecular weight modifier composition may be supported immediately after the metallocene compound is supported on the carrier on which the first cocatalyst is supported. In particular, according to the conventional prior art, the organo aluminum and precursors are first reacted with MA0 and then supported on silica. First, add titanene (Ti tani cene) to the MA0 solution The reaction of TMA and Ti tanocene in MAO to the reaction of Tibec reagent (Tebbe reagent) is made in-situ. The effect may be to react with the precursors. However, when preparing such a supported catalyst, the stability of the supported catalyst resulting from the heterogeneity of the MA0 solution according to the reactivity between the precursor and MA0, and the conventional Tebe reagent reaction are about 2 to 4 days in the present invention, for example, 3 Problems with reproducibility of catalyst properties can arise from shorter reaction times compared to days.

In particular, the present invention is a method in which the molecular weight regulator is added immediately after the metallocene compound catalyst precursor is added to silica loaded with a C 1 promoter such as MA0 to ensure uniformity of silica-MA0 itself, The regulator can also sufficiently increase the molecular weight even with a catalytic amount compared to the precursor. In addition, the present invention can prevent the occurrence of a problem of inhibiting the intrinsic activity of the precursor in a small amount of the molecular weight regulator. On the other hand, in the above-described metallocene catalyst, in particular, the common supported metallocene catalyst, it may further include a borate-based crab 2 co-catalyst of the formula (13):

[Formula 13]

T ⁺ [BQ ₄ ] ^"

In formula (13), T ⁺ is a + monovalent polyatomic ion, B is boron in the +3 oxidation state, Q is independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryl oxide group, Selected from the group consisting of hydrocarbyl groups, halocarbyl groups and halo-substituted hydrocarbyl groups, wherein Q has up to 20 carbons, but at less than one position Q is a halide group. By the use of such first and second cocatalysts, the molecular weight distribution of the finally produced polyolefin can be made more uniform, and the polymerization activity can be improved.

The first cocatalyst of Chemical Formula 12 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular or reticulated form, and specific examples of the first cocatalyst include methylaluminoxane (MA0) and ethylalumina. Noxyl acid, isobutyl aluminoxane or butyl aluminoxane. In addition, the C2 promoter of Formula 13 may be a borate-based compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt. Specific examples of such a second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate ， Methyltetracyclooctadecylammonium tetraphenylborate ， Ν, Ν-dimethylanilinium tetraphenylborate ， Ν, Ν-diethylanilinium tetraphenylborate ， ^ dimethyl (2,4,6-trimethylanilinium) tetraphenyl Borate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium, tetrakis (penta ¾ fluorophenyl) borate,

Tripropylammonium tetrakis (pentafluorophenyl) borate, tri (η-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate ， Ν , Ν-dimethylanilinium tetrakis (pentafluorophenyl) borate ， Ν, Ν-diethylaniliniumtetrakis (pentafluorophenyl) borate ， Ν, Ν-dimethyl (2,4,6-trimethylanilinium) Tetrakis (pentafluorophenyl) borate ，

Trimethylammonium tetrakis (2, 3, 4, 6-tetrafluorophenyl) borate,

Triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate tri (η-butyl) ammonium tetrakis ( 2,3,4,6-, tetrafluorophenyl) borate dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate Ν, Ν—dimethylanilinium ^■ tetrakis ( 2,3,4,6-tetrafluorophenyl) borate Ν, Ν-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate or Ν, Ν-dimethyl-(2,4 Borate compounds in the form of trisubstituted ammonium salts, such as 6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate; Dioctadecyl ammonium tetrakis (pentafluorophenyl) borate ， Borate compounds in the form of polyalkylammonium salts such as ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclonuxylammonium tetrakis (pentafluorophenyl) borate; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl And a borate compound in the form of a trisubstituted phosphonium salt such as) borate.

On the other hand, in the case of producing a common supported metallocene catalyst by using two or more kinds of the above-described metallocene compound and the first and second covalent metallocene compounds and the first and second cocatalysts, the carrier may be made of one metal. After the Rosene compound and the Crab 1 promoter are sequentially supported, the second metallocene compound and the Crab 2 promoter can be sequentially supported. In between these supporting steps, a washing step using a solvent may be further performed. On the other hand, according to another embodiment of the invention, as described above, the production of a polyolefin comprising the step of polymerizing the olethene-based monomer in the presence of a metallocene-supported catalyst carrying a specific molecular weight modifier with a metallocene compound on the carrier A method is provided.

The polymerizing of the olefin monomer may be performed by mixing at least one metallocene compound represented by one of Chemical Formulas 3 to 6 with a cyclopentadienyl metal compound of Chemical Formula 1 and an organoaluminum compound of Chemical Formula 2 below. For example, slurry polymerization of an olefinic monomer in the presence of a metallocene supported catalyst obtained by supporting together a molecular weight modifier composition obtained by stirring at 22.5 to 25 ^° C. for 50 to 108 hours, preferably 62 to 90 hours. Can be done in stages.

In the method for producing a polyolefin according to the embodiment, a polyolefin may be prepared by polymerizing any olefin monomer. Specific examples of the olefin monomer that can be used at this time include ethylene, propylene, 1-butene, 1-nuxene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-nucleene, 1-heptene, 1-decene , 1-Undecene, 1-dodecene, norbornene, ethylidenenorbornene, styrene, alpha -methylstyrene and 3- Chloromethyl styrene and the like. However, in one example of such a manufacturing method, polyethylene is produced using ethylene, or together with ethylene, propylene, 1-butene, 1-nuxene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1 An ethylene-alpha olefin copolymer may be prepared by copolymerizing alpha olefins such as -nuxene, 1-heptene, 1-decene, 1-undecene or 1-dodecene. In this case, the comonomer such as alpha olefin may be copolymerized by being used in an amount of about 30% by weight or less, or about 0 to 20% by weight, or about 0.01 to 15% by weight based on the total amount of the olefin monomer. have. As this amount of alpha olefins are copolymerized, the final polyolefins produced can exhibit excellent stress cracking resistance within a density range suitable for blow molding. However, when an excessively large amount of alpha olefin is used, the density of the polymer may be decreased, leading to a decrease in flexural strength.

In addition, the polymerization method of the above-described embodiment may be carried out in a slurry phase in an aliphatic hydrocarbon solvent such as nucleic acid, butane or pentane, for example. As the metallocene catalyst including the molecular weight modifier exhibits excellent solubility in such a solvent, they can be stably supplied to the dissolution and reaction system so that the polymerization process can proceed effectively, and poly having a large molecular weight and a wider molecular weight distribution can be obtained. Lepin can be produced effectively.

On the other hand, the above-described polymerization method of one embodiment using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reaction reactor or a solution reactor, homopolymerized with one olepin monomer or copolymerized with two or more monomers You can proceed.

The polymerization of the olefinic monomers may be performed by reacting at a temperature of about 25 to about 500 ^° C. and about 1 to about 100 kgf / cm ² for about 1 to about 24 hours. Specifically, the polymerization of the olefin monomer may be carried out at a temperature of about 25 to about 500 ° C, preferably about 25 to about 200 ^° C, more preferably about 50 to about 100 ^° C. The reaction pressure may also be carried out at about 1 to about 100 kgf / cm ² , preferably at about 1 to about 50 kgf / cm ² , more preferably at about 5 to about 40 kgf / cm ² .

According to the invention it is possible to maintain a high activity while having an excellent molecular weight increase effect of the polymer during olefin polymerization. In particular, of the present invention The catalytic activity calculated from the ratio of the weight (g) of the polymer produced per unit weight content (g) of the catalyst used in the process for producing the polyolefin based on the unit time (h) is not less than 1.0 kg / gCat-hr or 1.0 to 15 0 kg / gCat · hr, preferably 10.0 kg / gCat−hr or more, and more preferably 8.0 kg / gCat · hr or more. In particular, the present invention can effectively control the molecular weight of a single or common supported catalyst while using a small amount of the molecular weight regulator corresponding to the amount of catalyst of the metallocene precursor supported when preparing the metallocene supported catalyst. Existing conventional techniques have been shown to simply increase the molecular weight, but the present invention has the advantage of finely adjusting the polymer structure according to the amount of the molecular weight regulator while maintaining the polymerization conditions without activity degradation. On the other hand, according to another embodiment of the invention, there is provided a polyolefin prepared according to the production method of the above-described embodiment. Such a polyolefin may be preferably used for blow molding, injection molding, etc., as it has a molecular weight distribution in which a large molecular weight and a polymer elasticity increase to improve swell.

The polyolefin according to the present invention may have a large molecular weight of about 100,000 to 2,000,000 or about 110,000 to 1,500,000, about 120,000 to 700,000, about 150,000 to 550,000, about 200,000 to 450,000 by the action of the above-described molecular weight modifier, etc. The elasticity can be increased to have a molecular weight distribution that improves the swell. In particular, when preparing polyolefins through slurry polymerization or the like, the polyolefins may have a greater molecular weight of at least about 250,000, or at least about 280,000, at least about 300,000, at least about 330,000. In addition, the melt index (Ml 21.6 kg) of the polyolefin prepared through the slurry polymerization process or the like is 15.0 g / 10 m in or less, or 0.01 to 15 g / 10 min, preferably 10 g / 10 min or less, and more preferably 1 g /. can be iOmin or less. Due to such a large molecular weight and high polymer elasticity increases the molecular weight distribution of the swell (swell), can exhibit excellent mechanical properties and processability at the same time. In particular, according to the present invention it is possible to produce a polyolefin excellent in mechanical properties such as ESCR (Environmental Stress-Cracking Resistance), low temperature laminar strength with a high molecular weight. Such polyolefin may be used for blow molding, and may be used for injection molding, film, pipe or beam cap, and the like.

【Effects of the Invention】

As described above, according to the present invention, as the molecular weight distribution of the swell is improved due to the increase of the large molecular weight and the report molecule elasticity, a polyolefin which can be preferably used for blow molding or injection molding is more effectively produced. Provided is a method for producing a metallocene supported catalyst.

When the metallocene supported catalyst is used, the melt index is low, the molecular weight distribution is wide, and the high notch creep test (FNCT) is higher than the density or melt index, so that it is suitable for blow molding or injection molding. Particularly suitable polyolefins can be produced very effectively. 【Brief Description of Drawings】

1 is a graph showing the molecular weight distribution of a polymer for a polymerization reaction using a metallocene supported catalyst prepared according to Examples 10-12 and Comparative Example 4 (Brown: Test Example 10, Red: Test Example 11, Purple: Test Example 12, Blue: Comparative Test Example 4).

Figure 2 is a graph showing the molecular weight distribution of the polymer for the polymerization reaction using the metallocene supported catalyst prepared according to Comparative Example 3, Example 8 (red: test example 8, green: Comparative Test Example 3).

Figure 3 is a graph showing the molecular weight distribution of the polymer for the polymerization reaction using the metallocene supported catalyst prepared according to Comparative Example 2, Example 5 (red: Test Example 5, Blue: Comparative Test Example 2).

[Specific contents to carry out invention]

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the invention and the scope of the invention is not limited to the following examples. EXAMPLE

Synthesis Example 1

[Synthesis of t-Bu ^{^} OCCHg Csiy ^ rMez

t-Bu

^ Hunted Tetrahedron Lett using 6-chlorohexanol. 2951 (1988)) to prepare t-butyl-0- (CH ₂ ) ₆ -Cl, and reacted with NaC ₅ ¾ to obtain t-butyl- (C¾) ₆ -C ₅ H ₅ . (Yield 60¾>, bp 80 ^° C / 0.1 mmHg).

After dissolving 2.0 g (9.0 隱 ol) of t-butyl-0- (CH ₂ ) 6 -C ₅ H ₅ in THF at -78 ^° C, and slowly adding 1.0 equivalent of normal butyllithium (n-BuLi) thereto, The temperature was raised to room temperature, followed by reaction for 8 hours. This reaction solution was slowly added to a suspension solution of Zr (CH ₃ ) 2 (THF) ₂ (1.70 g, 4.5 nmol) / THF (30 mL) at -78 ^° C, followed by 6 hours at room temperature. It was further reacted to obtain a final reaction product.

The reaction product was dried in vacuo to remove all volatiles, followed by addition of nucleic acid (hexane) to the remaining oily liquid material, followed by filtration using a schlenk glass filter. The filtered solution was dried in vacuo to remove the nucleic acid, which was then added again to induce precipitation ^at low temperature (-20 ^° C.). The precipitate obtained was filtered at low temperature to give a white solid [t-Bu-0 (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound in a yield of 92>. The measured KEL and ¹³ C NMR data of [t-Bu_ 0 (C¾) ₆ -C ₅ H ₄ ] ₂ ZrCl _{2 obtained} were as follows.

¾ NMR (300 MHz, CDC1 ₃ ): 6.28 (t, J = 2.6Hz, 2H), 6.19 (t, J = 2.6Hz, 2H), 3.31 (tJ = 6.6Hz, 2H), 2.62 (t, J = 8 Hz, 2H), 1.7-1.3 (m, 8H), 1.17 (s, 9H)

¹³ C NMR (CDCls): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30. 14, 29. 18, 27.58, 26.00 Synthesis Example 2

At room temperature, 50 g of Mg (s) was added to a 10 L reactor, followed by 300 mL of THF.

After about 0.5 g of h was added, the reaction temperature was maintained at 50 ^° C. After the reaction was stabilized, 250 g of 6-t-buthoxyhexyl chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. As 6-t-butoxynucle chloride was added, it was observed that the reactor temperature rose about 4 to 5 degrees. Subsequently, the mixture was stirred for 12 hours while adding 6-t-secondary nucleus chloride.

After 12 hours of reaction, a black reaction solution was obtained. After taking 2niL of the resulting black solution, water was added to obtain an organic layer.-6-t-butoxyhexane was identified by MR, and Grignard (Gr ignard) was obtained from 6-t- appendic acid. The reaction was well done. Thus, 6-t-buthoxyhexyl magnesium chloride was synthesized.

After adding 500 g of MeSiCls and 1 L of THF to the reactor, the reactor temperature was-

It was made up to 20 ^° C. 560 g of the synthesized 6-t-butoxyhexyl magnesium chloride was added to the reaction vessel at a rate of 5 mL / min using a feed pump.

After the supply of the Grignard reagent was completed, the reaction mixture was stirred for 12 hours while slowly bringing the temperature to room temperature.

After 12 hours, it was confirmed that a white MgCl ₂ salt was produced. Nucleic acid

4 L was added to remove the salt through labdor i to obtain a filter solution. After adding the obtained filter solution to the reaction, at 70 ^° C. A yellow liquid could be obtained.

^'Could be a liquid through -NMR confirm that the desired methyl (6-t- appendix when haeksil) dichlorosilane (methyl (6-t- butoxyhexyl) dichlorosi lane) of the compound obtained.

匿 (CDCls): δ = 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s,

9H), l.Km, 2H), 0.7 (s, 3H)

Tetramethylcyclopentadiene 1.2 mole (150 g) and 2.4 L of THF were added to the reactor, and the reactor temperature was changed to -20 ^° C. 480 mL of n-BuLi was added to the reactor at a rate of 5, L / min using a feed pump. n—BuLi was added, followed by stirring for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, an equivalent of methyl (6-t-butoxy nucleosil) dichlorosilane (326 g, 350 mL) was added quickly to the reactor. The reaction mixture was stirred for 12 hours while slowly warming 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 back to the reactor, the nucleic acid was removed at 70 ^° C to obtain a yellow solution. The obtained yellow solution was confirmed to be a _methyl (6-t- appendage nucleus) (tetramethyl _{CpH) t} _ butylaminosilane _(methyl (6-t-butoxyhexyl KtetramethylCpH -butylaminosi lane) compound through ᅳ NM.

TiCl ₃ (THF) ₃ (n-BuLi and the ligand dimethyl (tetramethyl CpH) t-butylaminosilane (dimethyl (tetramethylCpH) t-butylaminosi lane) in the dilithium salt of -78 ^° C ligand synthesized in THF solution 10 μl ol) was added rapidly. The reaction solution was stirred for 12 hours while slowly releasing to room temperature at -78 ^° C.

After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 Pa ol) 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 THF was removed from the resulting reaction solution, the product was filtered by adding nucleic acid. The nucleic acid was removed from the filter solution obtained, followed by ¾-NMR, followed by desired [methyl (6-t-butyloxysil) silyl (η5-tetramethyl Cp) (t-butylamido)] TiCl ₂ ([methyl (6-t -butoxyhexyl) silyl (ri 5-tetramethylCp) (t- Butylamido)] TiCl _{2 It} was confirmed that the compound.

¾-NMR (CDCI3): δ = 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6G) 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), 0.7 (3, 3H)

3-1 Preparation of Ligand Compound

f Dissolve 2 g of luorene in 5 mL MTBE and 100 mL of hexane, add 5.5 mL of 2.5 M n-BuLi hexane solution in a dry ice / acetone bath ^. Stir overnight. 3.6 g of (6- (tert-butoxy) hexyl) dichloro (niethyl) silane was dissolved in 50 mL of nucleic acid (hexane), and the fluorene-Li slurry was transferred for 30 minutes under a dry ice / acetone bath and stirred at room temperature overnight. At the same time, 5, 8-di methyl -5, 10-di hydr 0 i ndeno [1, 2-b] i ndo 1 e (12 隱 ol, 2.8 g) was also dissolved in 60 mL of THF 2.5M n-BuLi hexane solut 5.5 mL of ion was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. NMR sampling of the reaction solution between f luorene and (6— (tert-butoxy) hexyl) dichloro (methyl) si lane to confirm the completion of the reaction, 5,8-dimethy 卜 5,10-dihydroindeno [l, 2-b] Indole-Li solut ions were transferred under dry ice / acetone bath. Stir overnight at room temperature. After the reaction, the organic layer was extracted with ether / water to remove residual moisture of the organic layer with MgS0 ₄ , and a ligand compound (Mw 597.90, 12 을 ol) was obtained. Two isomers were formed in 1H-NMR.

¾ NMR (500 MHz, d6 ^- benzene): -0.30--0.18 (3H, d), 0.40 (2H, m), 0.65-1.45 (8H, m), 1.12 (9H, d), 2.36-2.40 (3H , d), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21 (1H, d), 4.34-4.38 (1H, d), 6.90-7.80 (15H, m)

Preparation of 3-2 Metallocene Compound 7.2 g (12 ′ ol) of the ligand compound synthesized in 3-1 above was dissolved in 50 m of diethylether, and 11.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath, followed by stirring overnight at silver. Drying in vacuo gave a brown colored sticky oil. It was dissolved in toluene to obtain a slurry. ZrCl ₄ (THF) ₂ was prepared, and 50 mL of toluene was added to prepare a slurry. 50 mL of ZrCl ₄ (THF) ₂ was transferred to a luene slurry in a dry ice / acetone bath. The solution was changed to violet color at room temperature overnight. The reaction solution was filtered to remove LiCl. The toluene of the filtrate was removed by vacuum drying, and the nucleic acid was added thereto and sonicated for 1 hour. The slurry was filtered to obtain 6 g of a dark violet metallocene compound (Mw 758.02, 7.92) ol, yield 66 mol¾>) as a filtered solid. Two isomers were observed on 1H-NMR.

¾ NMR (500 MHz, CDC1 ₃ ): 1.19 (9H, d), 1.71 (3H, d), 1.50-1.70 (4H, m), 1.79 (2H, m), 1.98-2.19 (4H, m), 2.58 (3H, s), 3.38 (2H, m), 3.91 (3H, d), 6.66-7.88 (15H, m)

Synthesis Example 4 Preparation of Molecular Weight Control Agent i + 2 TIBAL

Bis (2-butylcyclopenta-2,4-diene-1-yl) titanium (IV) chloride (bis (2-butylcyclopenta-2,4-dien-yl) titanium (IV) in a 250 mL isometric flask chloride) 1.08 g (3 μl) was added and 50 mL of nucleic acid was stirred. 6 mL (6 睡 ol) of triisobutyl aluminum (1M in hexane) was added thereto, followed by stirring for 3 days at phase silver. After the solvent was removed in vacuo, a blue liquid mixture was obtained, which was oxidized or changed in color with reduced titanium. In the following blue mixture was used as it is without purification. ¾ NMR (CDCI ₃ , 500 MHz): 6.1-6.6 (br m, 8H), 2.2 (m, 4H), 1.0-1.8 (br m, 16H), 0.4 (br s, 24H) Synthesis Example 5: Molecular weight regulator Manufacture

2 TIBAL

Bis (2-ethylcyclopenta-2,4-diene-1-yl) titanium (IV) chloride (bis (2-ethylcyclopenta-2,4-dien ᅳ 1-yl) titanium (IV) in a 250 mL isometric flask chloride) 0.91 g (3 瞧 ol) was added and 50 mL of nucleic acid was stirred. 6 mL (6 隱 ol) of triisobutyl aluminum (1M in hexane) was added thereto, followed by stirring at room temperature for 3 days. After the solvent was removed in vacuo, a blue liquid mixture was obtained, which was oxidized and did not change color as the titanium was reduced. In the following blue mixture was used as it is without purification.

¾ NMR (CDCls, 500 MHz): 6.2-6.6 (br m, 8H), 1.0-1.8 (br m, 7H), 0.8 (br s, 24H) Synthesis Example 6 Preparation of Molecular Weight Control Agent

Bis (2- (6-t-butoxy-nuxyl) cyclopenta-2,3-diene-1-yl) titanium chloride (bis (2- (6-t-butoxy-hexyl) cyclopenta in a 250 mL isometric flask Add 1.68 g (3 誦 ol) of 2,4-dien-l-yl) titanium (IV) chloride), add 50 mL of nucleic acid and stir. Triisobutyl aluminum here 6 mL (6 mmol) of aluminum, 1M in hexane) was added thereto, and the resultant was stirred at room temperature for 3 days. After the solvent was removed in vacuo, a blue liquid mixture was obtained, which was oxidized and did not change color as the titanium was reduced. In the following blue mixture was used as it is without purification.

¾ NMR (CDCls, 500 腿 z): 6.31 (br m, 8H), 3.5 (m, 4Η), 1.1-1.9

(br m, 28H), 0.9 (br s, 18H), 0.3 (br s, 18H) Synthesis Example 7 Preparation of Molecular Weight Control Agent

\

+ 2 units

— ： 0.83 g of bis (cyclopentadienyl) titanium dichloride (bis) and 50 mL of nucleic acid were sequentially added to a 250 mL round bottom flask, followed by stirring. 6 mL of triisobutylalunium (1M in hexane) was added thereto, stirred at room temperature for 3 days, and then the solvent was removed in vacuo to obtain a green compound, which was oxidized as titanium reduced. Did not change color. In the following the green compound was used as it is without purification. '

¾ (CDCls, 500 MHz): 6.3-6.6 (br m, 10H), 1.2-1.8 (br m, 4H) 0.8 (br s, 18H).

Example 1 Preparation of Metallocene Supported Catalyst

First, silica (SYL0P0L 948, manufactured by Grace Davison) was dehydrated under vacuum at a temperature of 400 ^° C. for 15 hours.

After adding 10 wt% methylaluminoxane (MAO) / luene solution to 49.7 mL in a glass reaction machine, and adding 9.1 g of silica (SYL0P0L 948, manufactured by Grace Davison) at 40 ^° C, the reaction temperature was 80 ^° C. Stirring while raising to C. After the temperature After maintaining ^at 80 ^° C. 550 mg (0.1 誦 ol / gSi0 ₂ ) of the catalyst precursor prepared in Synthesis Example 1 was dissolved in 20 mL of toluene, 53 mg ( 10 m () l¾) of the precursor was put together and directly added to the reactor. After stirring for 2 hours, 948 mg (0.12 隱 ol / _g Si0 ₂ ) of anninium borate (N, N-dimethyl ani 1 inium tetraki s (pentaf luorophenyl) borate, AB) was dissolved in 20 mL of toluene. The solution was added and stirred at 40 ^° C for 2 hours. After the reaction was completed, the stirring was stopped, the toluene layer was separated and removed, and then the reduced pressure was reduced at 40 ^° C. to remove the remaining toluene to prepare a metallocene supported catalyst. Examples 2 and 3: Preparation of Metallocene Supported Catalyst

As shown in Table 1, the metallocene supported catalyst was prepared in the same manner as in Example 1, except that 160 mg (30 mol%) and 270 mg (50 mol%) of the molecular weight modifier were added. Prepared. Example 4 Preparation of Metallocene Supported Catalyst

As shown in Table 1, a metallocene supported catalyst was prepared in the same manner as in Example 1, except that 465 mg (0.1 μL / gSi) of the catalyst precursor prepared in Synthesis Example 2 was used. .

'

Examples 5 and 6: Preparation of Metallocene Supported Catalysts

As shown in Table 1, the metallocene supported catalyst was prepared in the same manner as in Example 4, except that the content of the molecular weight modifier was 160 mg (30 mol%) and 270 mg (50 mol%), respectively. Prepared. . Example 7 Preparation of Metallocene Supported Catalyst

. As shown in Table 1, a metallocene supported catalyst was prepared in the same manner as in Example 1, except that 690 mg (0.1 μl ol / gSi0 ₂ ) of the catalyst precursor prepared in Synthesis Example 3 was used. It was. Examples 8 and 9: Preparation of Metallocene Supported Catalysts

As shown in Table 1, a metallocene supported catalyst was prepared in the same manner as in Example 7, except that the content of the molecular weight modifier was 160 mg (30 mol) and 270 mg (50 mol%), respectively. It was. Example 10 Preparation of Metallocene Supported Catalysts

First, silica (SYL0P0L 948, manufactured by Grace Davi son) was dehydrated under vacuum at a temperature of 400 ^° C. for 15 hours.

A 10 wt% methylaluminoxane (MAO) / luene solution was added to 49.7 mL in a glass reactor, and silica (SYL0P0L 948, manufactured by Grace Davi son) was added at 40 ^° C. Stirring while stirring at ^° C. After lowering the temperature to 80！ after dissolving 520 mg (0.075 隱 ol / _g Si0 ₂ ) catalyst precursor prepared in Synthesis Example 3 in 20 mL of toluene, 53 mgdO mol¾ the molecular weight regulator prepared in Synthesis Example 4 Were put together and immediately put into the reaction machine. After stirring for 2 hours, after reacting 550 mg (0.1 隱 ol / gSi0 ₂ ) of the catalyst precursor prepared in Synthesis Example 1 at 40 ^° C. for 2 hours, aninium borate (N, N-dimethyl ani 1 Indium tetraki s (pentaf luorophenyl) borate, AB) 948 mg (l .2 隱 ol / gSi0 ₂ ) was pre-dissolved in 20 mL of toluene, added as a solution and stirred at 40 ^° C for 2 hours. After the reaction was completed, the stirring was stopped, the toluene layer was separated and removed, and then, the reduced pressure was removed at 40 ^° C to remove the remaining toluene to prepare a metallocene supported catalyst. Examples 11 and 12: Preparation of Metallocene Supported Catalysts

As shown in Table 1, the metallocene supported catalyst was prepared in the same manner as in Example 10, except that the content of the molecular weight modifier was 160 mg (30 mol%) and 270 mg (50 mol%), respectively. Prepared. Comparative Example 1: Preparation of Metallocene Supported Catalyst

First, silica (SYL0P0L 948, manufactured by Grace Davi son) was dehydrated under vacuum at a temperature of 400 ^° C. for 15 hours. Into the glass reactor, 10 wt% of methylaluminoxane (MAO) / luene solution was added to 49.7 mL, and 9.1 g of silica (SYL0P0L 948, manufactured by Grace Davison) was added at 40 ^° C., and the reactor temperature was increased to 80 ^° C. Stirring while raising. After lowering the temperature to 80 ^° C. 550 mg (0.1 讓 ol / gSi¾) of the catalyst precursor prepared in Synthesis Example 1 was dissolved in 20 mL of toluene and immediately added to the reactor. After stirring for 2 hours, 948 mg (1.2 mmol / gSi0 ₂ ) of anilinium borate (N, N-dimethylanilinium tetrakis (pentaf luorophenyDborate, AB)) was dissolved in 20 mL of toluene, and then added as a solution to 40 ^° C. After stirring, the reaction was terminated, the stirring was stopped, the toluene layer was separated and removed, and the remaining toluene was removed under reduced pressure at 40 ^° C., to prepare a metallocene supported catalyst. Preparation of supported catalyst

As shown in Table 1 below, 465 mg (0.1 μl ol / gSi0 ₂ ) of the catalyst precursor prepared in Synthesis Example ₂ and 690 mg (0.1 μl ol / gSi0 ₂ ) of the catalyst precursor prepared in Synthesis Example 3 were used, respectively. Except that, a metallocene supported catalyst was prepared in the same manner as in Comparative Example 1. Comparative Example 4: Preparation of Metallocene Supported Catalyst

Into the glass reactor, 10 wt% methylaluminoxane (MA0) / luene solution was added to 49.7 mL, and 9.1 g of silica (SYL0P0L 948, manufactured by Grace Davison) was added at 40 ^° C., and the reaction temperature was increased to 80 ^° C. Stirring while stirring. After lowering the temperature to 80 ^° C. 520 mg (0.075 匪 ol / gSi0 ₂ ) of the catalyst precursor prepared in Synthesis Example 3 was dissolved in 20 mL of toluene and added to the reaction vessel and stirred for 2 hours, the synthesis example 1 After reacting 550 mg (0.1 醒 ol / gSi0 ₂ ) catalyst precursor prepared at 2 ^° C. for 2 hours at 40 ^° C., 948 mg (0.12 mmol / gSi0 ₂ ) of anninium borate (N, N-dimethylanilinium tetrakis (pentaf luorophenyDborate, AB) ) Is dissolved in 20 mL of toluene, added in solution, and 40 ^° C for 2 hours. Stirred. After the reaction was completed, the stirring was stopped, the toluene layer was separated and removed, and the remaining toluene was removed by reducing the pressure at 40 ^° C to prepare a metallocene supported catalyst.

Polymerization test example 1

Using Parr reaction, 400 mL of nucleic acid was added to an isolated system filled with argon, and then 1 g of trimethylaluminum was dried to dry the reactor and discarded. After 400 mL of nucleic acid was filled in a reaction vessel, 0.5 g of triisobutylaluminum was added thereto. The supported catalyst prepared in Example 1 was improved to 10 mg in an argon-filled glove box and placed in a reaction vessel, followed by argon venting, followed by polymerization for 1 hour by making ethylene 30 bar pressure at 78 ^° C. Polymerization Test Examples 2-12

As shown in following Table 1, except that each used a supported catalyst prepared in Examples 2 to _{12: To} a slurry polymerization conducted in the same manner as in Test Example 1 polymerization. Polymerization Comparative Test Examples 1-4

As shown in Table 1, slurry polymerization was carried out in the same manner as in Test Example 1, except that each of the supported catalysts prepared in Comparative Examples 1 to 4 was used. Polymerization Comparative Test Examples 5-8

As shown in Table 1 below, each of the catalysts prepared in Comparative Examples 1 to 4 was used, and 1 mg (0.6 瞧 ol / _g Si0 ₂ ) of the molecular weight regulator prepared in Synthesis Example 4 was further added. A slurry polymerization was carried out in the same manner as in Test Example 1, except that it was added to. Experimental Example

Polymer property evaluation test example

The properties of the polyethylenes prepared in Polymerization Test Examples 1 to 12 and Polymerization Comparative Test Examples 1 to 4 were measured by the following methods, and the results are shown in Table 1 below. a) Molecular weight (Mw): It measured by weight average molecular weight using gel permeation chromatography (GPC). b) Molecular weight distribution (PDI): The weight average molecular weight was measured by gel permeation chromatography (GPC) divided by the number average molecular weight. c) Catalytic activity: 0.5 g of TMA was added to the reactor, dried, and 400 mg of nucleic acid was added to about 100 mg of the catalyst with alkyl aluminum and a molecular weight modifier (丽 E). After running for 1 hour, the polymer was obtained, dried after the filter, weighed, and then the catalytic activity was measured per unit time (hr). TABLE 1

Coupling catalyst 丽 E active Mw PDI 丁 ᄇ ^{1 "} (gPE /

(mol) gCat / hr)

Carrier /

Supported catalyst

Test Example 1 Precursor 1/10 ^* 10.4 128,000 _. 2.2 slurry synthesis

soluble 匪

Carrier /

^ Paper catalyst

Test Example 2 Catalyst Precursor 1/30 ^* 10.1 252,000 2.5 Slurry Polymerization

soluble 匪

Carrier /

Supported catalyst

Test Example 3 Catalyst Precursor 1/50 ^* 9.8 281,000 2.4 Slurry Polymerization

soluble MWE

Carrier / ^{· ■}

Supported catalyst

Test Example 4 Catalyst Precursor 2/10 ^* 2.6 594,000 2.4 Slurry Polymerization

soluble MWE

Supported catalyst carrier /

Test Example 5 30 ^* 2.3 660,000 2.3 slurry polymerization catalyst precursor 2 / soluble MWE

Carrier /

Supported catalyst

Test Example 6 Catalyst Precursor 2/50 ^* 1.8 780,000 2.3 slurry polymerization

soluble MWE

Carrier /

Supported catalyst

Test Example 7 Catalyst Precursor 3/10 ^* 2.3 791,000 3.4 Slurry Consolidation

soluble 丽 E

Carrier /

Supported catalyst

Test Example 8 Catalyst Precursor 3/30 ^* 2.0 972,000 3.1 Slurry Consolidation

soluble MWE

Carrier /

Supported catalyst

Test Example 9 Catalyst Precursor 3/50 ^* 1.5 1,020,900 3.1 Slurry Polymerization

soluble MWE

Carrier /

Test Example Supported Catalyst Catalyst Precursor 1 (0.1)

10 ^* 11.6 .. 273,000 3.4 10 slurry increased +3 (0.075) /

soluble MWE

Carrier /

Test Example Supported Catalyst Catalyst Precursor 1 (0.1)

30 ^* 11.3 318,000 3.9 11 slurry polymerization +3 (0.075) /

soluble MWE

Carrier /

Test Example Supported Catalyst Catalyst Precursor 1 (0.1)

50 ^* 11.5 298,000 3.3 12 slurry increase +3 (0.075) /

soluble 丽 E

Comparative Supported Catalyst Carrier /-10.1 103,100 2.1 Test Example 1 Slurry Polymerization Catalyst Precursor 1

Comparative Supported Catalyst Carrier /-2.8 553,000 2.5 Test Example 2 Slurry Polymerization Catalyst Precursor 2

Comparative Supported Catalyst Carrier /

2.3 693,000 3.6 Test Example 3 Slurry Consolidation Catalyst Precursor 3

Carrier /

Comparison

Catalyst Precursors 1 (0.1)-11.1 263,000 3.6 Test Example 4 Slurry Polymerization

+3 (0.075)

Comparative Supported Catalyst Carrier /

600 "6.3 228,000 2.2 Test Example 5 Slurry Consolidation Catalyst Precursor 1

Comparative Supported Catalyst Carrier /

600 "1.3 710,000 2.3 Test Example 6 Slurry Polymerization Catalyst Precursor 2

Comparative Supported Catalyst Carrier /

600 "1.0 730,000 3.4 Test Example 7 Slurry Polymerization Catalyst Precursor 3

Carrier /

Comparative supported catalyst

Catalyst Precursor 1 (0.1) 600 "7.3 293,000 3.2 Test Example 8 Slurry Polymerization

+3 (0.075)

Using a molecular weight adjusting agent after being supported on the support: ^- Test Examples 1 to 12

"Comparative Test Examples 5 to 8: The amount of -6 equivalents to the precursor of soluble 丽 E was added to the polymerization process as a molecular weight regulator.

In addition, the molecular weight distribution graph of the polymer for the polymerization reaction using the metallocene supported catalyst prepared according to Examples 10-12 and Comparative Example 4 is shown in FIG. And (brown: Test Example 10, Red: Test Example 11, Purple: Test Example 12, Blue: Comparative Test Example 4), and a polymerization reaction using a metallocene supported catalyst prepared according to Comparative Example 3 and Example 8. The molecular weight distribution graph of the polymer is shown in Figure 2 (red: Test Example 8, Green: Comparative Test Example 3), Comparative Example 2, of the polymer against the polymerization reaction using the metallocene supported catalyst prepared according to Example 5 The molecular weight distribution graph is shown in FIG. 3 (red: test example 5, blue: comparative test example 2). Here, X axis is dlogwf / dlogM, y axis is logM, the vertical axis is the Intensity axis of the polymer and the horizontal axis is the molecular weight axis of the polymer.

According to the molecular weight distribution graph of these polymers, the present invention is less active fluctuations compared to the prior art, and it can be seen that the molecular weight fluctuations fluctuate depending on the amount of the regulator, thereby enabling fine tuning in preparing the supported catalyst. have. In particular, in the case of Figure 2, when the input of the existing molecular weight regulator during the polymerization, the activity deterioration is severe and the portion of the increase in molecular weight was not large, but it was confirmed that the increase in molecular weight and activity is maintained to some extent by the supported catalyst. In addition, it can be seen that the polymer peaks move toward the polymer and the bimodal opening is narrowed to a single rod according to the change of the molecular weight regulator. This shows that the polymer elasticity, which is important in blow molding, is increased and thus the swell is changed to a model that improves the physical properties, thereby making the polymer of good orientation.

As shown in Table 1, according to the present invention, while having an excellent molecular weight increase effect of the polymer during olefin polymerization, it is possible to obtain an excellent effect of not causing a decrease in activity or copolymerizability. In particular, when an excess molecular weight regulator enters, the non-reflective regulator may be expressed while entering the reaction step again in the recovery process. In this case, the process may be shaken by an undesired polymerization process, so adding a molecular weight regulator in a reaction vessel is not a commercially appropriate method.

Moreover, as in Comparative Test Examples 5 to 8, the use of a molecular weight regulator during the polymerization process is not good in terms of reaction efficiency, and in the case of an actual mass production plant, reaction is caused by recycling raw materials. Unintentional action on other reaction processes can lead to unwanted polymerization processes. That is, the molecular weight control agent introduced during the polymerization may have instability in the overall polymerization process, but may have a molecular weight control effect at the laboratory level, but may cause process instability in a system of actual mass production scale. The present invention used a molecular weight regulator of the catalytic amount relative to the precursor in order to actively solve this problem and has the advantage of almost no side effects due to the molecular weight regulator in the actual plant application.

Claims

[Claim]

[Claim 1]

Preparing a molecular weight modifier composition by mixing a cyclopentadienyl metal compound of Formula 1 with an organoaluminum compound of Formula 2 and stirring at room temperature for 50 to 108 hours; And

Supporting at least one metallocene compound represented by one of the following Chemical Formulas 3 to 6 and the molecular weight modifier composition on a carrier;

Method for producing a metallocene supported catalyst comprising:

[Formula 1]

(R ^ Cp ^ CR ^ Cp ^ M ^ s

Cp ¹ and Cp ² in Formula 1 are each independently a ligand comprising a cyclopentadienyl group, an indenyl group, or a fluorenyl group; R ¹ and R ² are each independently a substituent of Cp ¹ and Cp ² , hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms, Aryl having 6 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, heteroalkenyl having 2 to 20 carbon atoms, heteroalkylaryl having 6 to 20 carbon atoms, heteroarylaryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms, ; M ⁴ is a Group 4 transition metal element; X is halogen,

[Formula ² ]

R¾ ⁴ R ⁵ A1

In formula (2), R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 4 to 20 carbon atoms or halogen, at least one of R ³ , R ⁴ and R ⁵ is an alkyl group having 4 to 20 carbon atoms,

[Formula 3]

In Chemical Formula 3,

M ¹ is a Group 4 transition metal;

Cp ⁵ and Cp ⁶ 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 One, these are May be substituted with a hydrocarbon having 1 to 20 carbon atoms;

R ^a and R ^b are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 Alkenyl to C20, alkyl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;

Z ¹ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

n is 1 or 0;

[Formula 4]

(Cp ⁷ R ^c ) _m B ¹ (Cp ⁸ R ^d ) M ² Z ² ₃ -m

In Chemical Formula 4,

M ² is a Group 4 transition metal;

Cp ⁷ and Cp ⁸ are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, tetrahydro-1-indenyl and fluorenyl radicals; They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;

R ^c and R ^d are the same as or different from each other, and independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ² is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to ^" C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkyl Lidene, a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy; B ¹ is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp¾ ^c ring with the Cp ⁴ R ^d ring or crosslinks one Cp ⁴ R ^d ring with M ² or Is a combination of;

m is 1 or 0;

[Formula 5]

(Cp ⁹ R ^e ) B ² (J) M ³ Z ³ ₂

In Chemical Formula 5,

M ³ is a Group 4 transition metal;

Cp ⁹ is any one selected from the group consisting of cyclopentadienyl indenyl, 4,5,6,7-tetrahydro-1'intenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms And;

R ^e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl Arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;

Z ³ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , optionally substituted amino group, C2 to C20 alkoxy alkyl, or C7 to C40 aryl alkoxy ^'; ᅳ

Any one selected from the group, the R ^f ¾ alkyl or substituted aryl,

In Chemical Formula 6,

A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 arginate, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 C20 alkoxyalkyl group, C3 To C20 heterocycloalkyl group, or C5 to C20 heteroaryl group;

D is — 0-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, C1 to An alkyl group of C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20;

L is a C1 to C10 straight or branched chain alkylene group;

B is carbon, silicon or germanium;

Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group,

C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;

M is a Group 4 transition metal;

X ¹ and X ² are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group Or a C1 to C20 alkoxy group or a C1 to C20 sulfonate group;

7a, 7b, or 7c, except that C ¹ and C ² are both 7g;

[

[

In Formulas 7a, 7b, and 7c, R1 to R17 and R1 'to R9' are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkyl Silyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, Two or more adjacent to each other of R10 to R17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

[Claim 2]

The method of claim 1,

The supporting step is a method for producing a metallocene supported catalyst consisting of a mixture of the carrier, metallocene catalyst, molecular weight regulator composition and stirred for 1 to 12 hours at a temperature of 30 to 100 ^° C.

[Claim 3]

The method of claim 1,

The molecular weight regulator composition is a method for producing a metallocene supported catalyst to be supported in a content of about 1 to 85 mol> based on the total amount of the metallocene compound.

[Claim 4]

According to claim 1,

In Formula 1, R ¹ and R ² are each independently selected from the group consisting of hydrogen, methyl, ethyl, butyl, and t-subspecific nuclear chambers. [Claim 5]

The method of claim 1,

In Formula 2, R ³ , R ⁴ , and R ⁵ are each independently an isobutyl group.

[Claim 6]

The method of claim 1,

M ⁴ in the formula (1) is a method for producing a metallocene supported catalyst that is selected from the group consisting of titanium, zirconium, and hafnium.

[Claim 7]

In U,

The olefin monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene ， 1- tetradecene ， 1—nuxadecene, 1-aitosen, norbornene, norbornadiene, ethylidenenorbornene phenylnorbornene, vinylnorbornene, dicyclopentadiene ， 1，4—butadiene ， 1，5- A method for producing a metallocene supported catalyst comprising at least one monomer selected from the group consisting of pentadiene 1,6-nuxadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

[Claim 8]

The method of claim 1,

The molecular weight regulator composition is a method for producing a metallocene supported catalyst comprising a compound represented by the following formula (8), (9), (10) or (11).

[Formula 9]

[Claim 9] The method of claim 1,

The carrier is a method for producing a metallocene supported catalyst is selected from the group consisting of silica, silica-alumina, and silica-magnesia. [Claim 10]

In U,

The carrier is a method of preparing a metallocene supported catalyst, which is supported with an aluminum-containing first cocatalyst of the formula (12):

[Formula 12]

-[Al (R ¹⁸ ) -0-] _n -In formula (12), each R ¹⁸ is independently a halogen, a halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and n is an integer of 2 or more.

[Claim 11]

The method of claim 10,

A method for producing a metallocene supported catalyst in which a molecular weight modifier composition is supported immediately after carrying a metallocene compound on a carrier on which the first cocatalyst is supported.

The method of claim 1,

A method for preparing a metallocene supported catalyst, which further supports a borate-based second cocatalyst of the formula (13).

[Formula 13]

T ⁺ [BQ ₄ ] ^"

In formula (13), T ⁺ is a + monovalent polyatomic ion, B is boron in +3 oxidation state, Q is independently a hydride group, dialkylamido group, halide group, alkoxide group, aryloxide group, hydro Selected from the group consisting of a carbyl group, a halocarbyl group, and a halo-substituted hydrocarbyl group, wherein Q has up to 20 carbons, but at less than one position Q is a halide group. [Claim 13]

A process for producing a polyolefin comprising polymerizing an olefin monomer in the presence of a metallocene supported catalyst prepared according to any one of claims 1 to 12.

[Claim 14]

The method of claim 13,

The step of polymerizing the ellepin monomer may be carried out in the presence of a metallocene supported catalyst carrying a molecular weight modifier composition comprising a reaction product of a metallocene compound, a cyclopentadienyl metal compound, and an organoaluminum compound on a carrier. Method for producing a polyolefin consisting of the step of slurry polymerization. [Claim 15]

Polyolefin prepared according to the polyolefin production method according to claim 13.