KR101670468B1 - Method for preparing polyolfin and polyolefin prepared therefrom - Google Patents

Abstract

The present invention relates to a process for the production of polyolefins and to polyolefins prepared therefrom. According to the present invention, there is provided a method for more effectively producing a polyolefin having a large molecular weight and a broad multi-branched molecular weight distribution. The polyolefin according to the production method of the present invention is excellent in mechanical properties and processability, and can be suitably applied particularly for blow molding.

Description

METHOD FOR PREPARING POLYOLFIN AND POLYOLEFIN PREPARED THEREFORM Technical Field [1] The present invention relates to a polyolefin,

The present invention relates to a process for the production of polyolefins and to polyolefins prepared therefrom.

In general, metallocene catalysts are more easily used to control the molecular weight and molecular weight distribution of polyolefins than conventional Ziegler-Natta catalysts, and can control the distribution of comonomers in the polymer, and are used to produce polyolefins and the like that have improved mechanical properties and processability simultaneously come. However, polyolefins prepared using metallocene catalysts suffer from poor processability due to their narrow molecular weight distribution.

Generally, the wider the molecular weight distribution, the higher the degree of decrease in viscosity with shear rate, and the better the workability in the machining area. The polyolefin prepared with the metallocene catalyst, due to the relatively narrow molecular weight distribution, There is a disadvantage in that the extrusion productivity and the blowing productivity are lowered. In particular, the bubble stability is significantly lowered during the blow molding process, and the surface of the produced molded article is uneven, resulting in lower transparency.

Thus, a multi-stage reactor including a plurality of reactors has been used in the past to obtain polyolefins and the like having a wide multi-molecular weight distribution with a metallocene catalyst, and through each polymerization step in such a plurality of reactors, And a large molecular weight at the same time.

However, due to the high reactivity of the metallocene catalyst, it is difficult to properly polymerize in the subsequent reactor depending on the duration of polymerization in the reactor at the front end, etc. As a result, it is difficult to obtain a polyolefin having a sufficiently large molecular weight and a broader multi- It is a fact that there was a limit to manufacturing. As a result of having a large molecular weight and a broader multimolecular molecular weight distribution, it is continuously required to develop a technique capable of simultaneously satisfying mechanical properties and processability, and more effectively producing a polyolefin which can be preferably used for blow molding have.

The present invention is intended to provide a method for more effectively producing a polyolefin having a large molecular weight and a broad multi-branched molecular weight distribution.

Further, the present invention is to provide a polyolefin which is produced by the above-mentioned method, and is particularly applicable for blow molding and the like.

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상기 제 2 메탈로센 화합물은 각각 하기 화학식 3으로 표시되는 화합물인, 폴리올레핀의 제조 방법이 제공된다:
[화학식 3]
(Cp¹R^a)_n(Cp²R^b)M¹Z¹ _3-n
상기 화학식 3에서,
M¹은 4족 전이금속이고;
Cp¹ 및 Cp²는 서로 동일하거나 상이하고, 각각 독립적으로 시클로펜타디엔닐, 인데닐, 4,5,6,7-테트라하이드로-1-인데닐, 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고, 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며;
R^a 및 R^b는 서로 동일하거나 상이하고, 각각 독립적으로 수소, C1 내지 C20의 알킬, C1 내지 C10의 알콕시, C2 내지 C20의 알콕시알킬, C6 내지 C20의 아릴, C6 내지 C10의 아릴옥시, C2 내지 C20의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C8 내지 C40의 아릴알케닐, 또는 C2 내지 C10의 알키닐이고;
Z¹은 할로겐 원자, C1 내지 C20의 알킬, C2 내지 C10의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C6 내지 C20의 아릴, 치환되거나 치환되지 않은 C1 내지 C20의 알킬리덴, 치환되거나 치환되지 않은 아미노기, C2 내지 C20의 알킬알콕시, 또는 C7 내지 C40의 아릴알콕시이고;
n은 1 또는 0 이다.According to the present invention,
In the presence of a first mixed metallocene catalyst comprising at least one first metallocene compound, at least one second metallocene compound, a co-catalyst compound, and a carrier, the first olefinic monomer- Stage 1; And
A second mixed supported metallocene catalyst comprising at least one of the first metallocene compound, at least one second metallocene compound, a co-catalyst compound, and a carrier in the reaction mixture of the first step, And a second step of further polymerizing and polymerizing a second olefin-based monomer;
Wherein the first metallocene compound is a compound of one of the following structural formulas,

;
Wherein the second metallocene compound is a compound represented by the following formula 3, respectively:
(3)
(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹³ _-n
In Formula 3,
M ¹ is a Group 4 transition metal;
Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^a and R ^b are the same or different and are each independently selected from the group consisting of hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 C20 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z ¹ represents a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
n is 1 or 0;

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According to the present invention, there is provided a method for more effectively producing a polyolefin having a large molecular weight and a broad multi-branched molecular weight distribution. The polyolefin according to the production method of the present invention is excellent in mechanical properties and processability, and can be suitably applied particularly for blow molding.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a process diagram schematically showing a production process of a polyolefin according to an embodiment of the present invention. FIG.

Hereinafter, a method of producing a polyolefin according to embodiments of the present invention and a polyolefin produced from the method will be described in detail.

Prior to that, unless explicitly stated throughout the specification, the terminology is used merely to refer to a specific implementation and is not intended to limit the invention. And, the singular forms used herein include plural forms unless the phrases expressly have the opposite meaning.

Also, the meaning of "includes" embodies certain features, areas, integers, steps, operations, elements or components, and does not exclude the addition of other specific features, areas, integers, steps, operations, elements, or components.

And, terms including ordinal numbers such as "first" or "second" can be used to describe various elements, and the elements are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may also be referred to as a second component, and similarly, the second component may also be referred to as a first component.

On the other hand, metallocene compounds are generally excellent in reactivity as compared with Ziegler catalysts, but have low mileage of catalysts and are applied in a cascade mode polymerization method. However, in the case of the multistage mode polymerization method, it is difficult to control the operating conditions for each reactor, and production of a bimodal polyolefin having homogeneous physical properties (or satisfying both workability and mechanical properties) due to unbalanced supply of the monomer compound . In addition, catalysts known to be capable of synthesizing high molecular weight polyolefins have relatively low activity, resulting in a problem of deteriorating the overall productivity.

As a result of continuous investigation by the inventors of the present invention, it has been found that, in the multistage mode polymerization method using the mixed supported metallocene catalyst, the mixed supported metallocene catalyst and the molecular weight adjusting agent are added to the reactor after the first step, It has been confirmed that the control of the polymerization method can be facilitated and the operation of the multistage mode can be performed more smoothly. In particular, when the type of mixed supported metallocene catalyst is different from that of the initially loaded mixed supported metallocene catalyst (for example, the amount of supported metallocene compound, the amount of supported metallocene compound The physical properties of the resulting polymer can be more easily controlled. In addition, by this method, a polyolefin having a large molecular weight and a wide multimolecular molecular weight distribution can be produced more effectively. The polyolefin produced by this method is excellent in mechanical properties and processability, and can be suitably applied particularly to blow molding.

I. Polyolefin  Manufacturing method

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상기 제 2 메탈로센 화합물은 각각 하기 화학식 3으로 표시되는 화합물인, 폴리올레핀의 제조 방법이 제공된다:
[화학식 3]
(Cp¹R^a)_n(Cp²R^b)M¹Z¹ _3-n
상기 화학식 3에서,
M¹은 4족 전이금속이고;
Cp¹ 및 Cp²는 서로 동일하거나 상이하고, 각각 독립적으로 시클로펜타디엔닐, 인데닐, 4,5,6,7-테트라하이드로-1-인데닐, 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고, 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며;
R^a 및 R^b는 서로 동일하거나 상이하고, 각각 독립적으로 수소, C1 내지 C20의 알킬, C1 내지 C10의 알콕시, C2 내지 C20의 알콕시알킬, C6 내지 C20의 아릴, C6 내지 C10의 아릴옥시, C2 내지 C20의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C8 내지 C40의 아릴알케닐, 또는 C2 내지 C10의 알키닐이고;
Z¹은 할로겐 원자, C1 내지 C20의 알킬, C2 내지 C10의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C6 내지 C20의 아릴, 치환되거나 치환되지 않은 C1 내지 C20의 알킬리덴, 치환되거나 치환되지 않은 아미노기, C2 내지 C20의 알킬알콕시, 또는 C7 내지 C40의 아릴알콕시이고;
n은 1 또는 0 이다.According to this embodiment of the present invention,
In the presence of a first mixed metallocene catalyst comprising at least one first metallocene compound, at least one second metallocene compound, a co-catalyst compound, and a carrier, the first olefinic monomer- Stage 1; And
A second mixed supported metallocene catalyst comprising at least one of the first metallocene compound, at least one second metallocene compound, a co-catalyst compound, and a carrier in the reaction mixture of the first step, And a second step of further polymerizing and polymerizing a second olefin-based monomer;
Wherein the first metallocene compound is a compound of one of the following structural formulas,

;
Wherein the second metallocene compound is a compound represented by the following formula 3, respectively:
(3)
(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹³ _-n
In Formula 3,
M ¹ is a Group 4 transition metal;
Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^a and R ^b are the same or different and are each independently selected from the group consisting of hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 C20 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z ¹ represents a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
n is 1 or 0;

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That is, a method for producing a polyolefin according to an embodiment of the present invention includes the first step and the second step as the polymerization step, and in particular, the second step includes the step of mixing the first hybrid supported metal A second hybrid supported metallocene compound, a molecular weight modifier and a molecular weight modifier are additionally added to the catalyst. Such a process for producing a polyolefin enables the production of a polyolefin having a large multimolecular weight distribution as well as a polyolefin having a large molecular weight. Further, by changing the types of the first hybrid supported metallocene catalyst and the second hybrid supported metallocene catalyst, the physical properties of the produced polyolefin can be easily controlled and, ultimately, a polyolefin having balanced mechanical properties and processability Can be provided.

According to an embodiment of the present invention, the first hybrid supported metallocene catalyst and the second hybrid supported metallocene catalyst may be the same or different from each other. For example, when the types of the first and second hybrid supported metallocene catalysts are the same, problems of low productivity due to low mileage of the metallocene compound can be solved, and if necessary, polyolefins having a larger molecular weight Can be produced. When the types of the first and second hybrid supported metallocene catalysts are different, as described above, the physical properties of the produced polyolefin can be easily controlled, and a polyolefin having a wider multi-molecular weight distribution can be produced .

According to an embodiment of the present invention, the types of the first hybrid supported metallocene catalyst and the second hybrid supported metallocene catalyst are not particularly limited and conventional catalysts can be applied to the present invention .

However, according to an embodiment of the present invention, the first hybrid supported metallocene catalyst comprises at least one first metallocene compound represented by the following general formula (1), at least one second metallocene compound, Carrier: < RTI ID = 0.0 >

[Chemical Formula 1]

In Formula 1,

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

D is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;

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

B is carbon, silicon or germanium;

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

M is a Group 4 transition metal;

X ₁ and X ₂ are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a 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 or different and each independently to formula 2a, 2b or formula to each other is represented by one of Formula 2c, stage, -C ₁ - And -C ₂ - are both the formula (2c);

 (2a)

(2b)

[Chemical Formula 2c]

In the above formulas (2a), (2b) and (2c)

R ₁ to R ₁₇ and R ₁ 'to R ₉ ' are the same or different and each independently represents hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a silyl group of C20, C1 to C20 alkoxy silyl group, an aryl group of C1 to C20 alkoxy group, C6 to C20 aryl group, a C7 to an alkylaryl group of C20, or a C7 to C20 of the R ₁₀ to R ₁₇ Two or more of which are adjacent to each other may be connected to form a substituted or unsubstituted aliphatic or aromatic ring.

In the above Formula 1, examples of the Group 4 transition metal (M) include, but are not limited to, titanium, zirconium, and hafnium.

In the general formula (1), A represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert- butyl group, a methoxymethyl group, a tert- A 1-methyl-1-methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group.

In Formula 1, B may preferably be silicon.

In Formula 1, L may be preferably a straight or branched alkylene group having 4 to 8 carbon atoms; The alkylene group may be substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

R ₁ to R ₁₇ and R ₁ 'to R ₉ ' each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert- Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a phenyl group, a halogen group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, Period, or ethoxy group.

The metallocene compound of the above formula (1) forms a structure in which an indeno indole derivative and / or a fluorene derivative is bridged by a bridge, and a non-covalent electron pair Thereby supporting a high Lewis acid property on the surface of the carrier and exhibiting a high polymerization activity even when carried. In addition, the activity is high due to the electron-rich indenoindole group and / or the fluorene group, and not only the hydrogen reactivity is low due to the appropriate steric hindrance and the electronic effect of the ligand, and high activity can be maintained even in the presence of hydrogen have. In addition, it stabilizes beta-hydrogen in the polymer chain of nitrogen molecules of indanediol derivatives by hydrogen bonding to inhibit beta-hydrogen elimination, thereby enabling the provision of polyolefins having an ultra-high molecular weight.

Also, when a polymerization reaction including hydrogen is carried out in order to produce a polyolefin having a high molecular weight and a broad molecular weight distribution, the first metallocene compound represented by the formula (1) exhibits low hydrogen reactivity and still exhibits high activity It is possible to polymerize an olefinic polymer having an extremely high molecular weight. Accordingly, the first metallocene compound enables the production of a polyolefin having high molecular weight characteristics without deterioration in activity even when it is used in combination with a catalyst compound having other characteristics.

According to one embodiment of the present invention, the first metallocene compound may be a compound represented by one of the following structural formulas, but is not limited thereto.

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According to an embodiment of the present invention, the compound of Formula 1 may be prepared by ligating an indenoindole derivative and / or a fluorene derivative with a bridge compound to form a ligand compound, and then performing metallation by introducing a metal precursor compound .

The method for producing the first metallocene compound will be described in the following Examples.

According to an embodiment of the present invention, the second metallocene compound may be selected from compounds represented by the following Chemical Formulas 3 to 5:

(3)

(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹ _{3 -n}

In Formula 3,

M ¹ is a Group 4 transition metal;

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

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

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

n is 1 or 0;

[Chemical Formula 4]

(Cp ³ R ^c ) _m B ¹ (Cp ⁴ R ^d ) M ² Z ² _{3 -m}

In Formula 4,

M ² is a Group 4 transition metal;

Cp < ³ > and Cp < ⁴ > are the same or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical , Which may be substituted with hydrocarbons having 1 to 20 carbon atoms;

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

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

B ¹ is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom containing radical which bridges the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or cross-links one Cp ⁴ R ^d ring to M ² Or a combination thereof;

m is 1 or 0;

[Chemical Formula 5]

(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂

In Formula 5,

M ³ is a Group 4 transition metal;

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

R ^e is hydrogen, C 1 to C 20 alkyl, C 1 to C 10 alkoxy, C 2 to C 20 alkoxyalkyl, C 6 to C 20 aryl, C 6 to C 10 aryloxy, C 2 to C 20 alkenyl, C 7 to C 40 alkylaryl , C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

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

B ² is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radical which cross-links the Cp ⁵ R ^e ring with J, or a combination thereof;

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

In the formula (4), when m is 1, it means that a Cp ³ R ^c ring, a Cp ⁴ R ^d ring or a Cp ⁴ R ^d ring and M ² are bridged by B ¹ , and m is 0 Quot; refers to the structure of the non-crosslinked compound.

The second metallocene compound represented by Formula 3 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

The second metallocene compound represented by Formula 4 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

The second metallocene compound represented by the general formula (5) may be, for example, a compound represented by the following structural formula, but is not limited thereto.

Wherein the mixed supported metallocene catalyst comprises at least one of the first metallocene compounds represented by Formula 1 and at least one second metallocene compound selected from the compounds represented by Formulas 3 to 5 Together with a co-catalyst compound.

The first metallocene compound represented by the formula (1) of the hybrid supported metallocene catalyst contributes mainly to the formation of a high molecular weight copolymer having a high short chain branch (SCB) content, and the second metallocene compound represented by the formula Schengen compounds can contribute to the production of low molecular weight copolymers with low SCB content. In addition, the second metallocene compound represented by the general formula (4) or (5) can contribute to the production of a low molecular weight copolymer having an intermediate SCB content.

According to an embodiment of the present invention, the hybrid supported metallocene catalyst may include at least one first metallocene compound represented by Formula 1 and at least one second metallocene compound represented by Formula 3.

According to another embodiment of the invention, the hybrid supported metallocene catalyst comprises, in addition to at least one first metallocene compound of formula (1) and at least one second metallocene compound of formula (3) And at least one second metallocene compound represented by the general formula (5).

In the hybrid supported metallocene catalyst, the first metallocene compound forms a ligand structure in which an indenoindole derivative and a fluorene derivative are bridged by a bridge compound, and a non-covalent electron pair capable of acting as a Lewis base in the ligand structure Thereby supporting the carrier on the surface having Lewis acid properties and exhibiting high polymerization activity even when carried. In addition, the activity is high due to the electron enrichment of the indenoindole group and / or the fluorene group, and not only the hydrogen reactivity is low due to the appropriate steric hindrance and the electronic effect of the ligand, and the high activity is maintained even in the presence of hydrogen. Therefore, when a hybrid supported metallocene catalyst is prepared using such a transition metal compound, it is possible to polymerize an ultrahigh molecular weight olefin polymer by stabilizing the beta-hydrogen of the polymer chain in which the nitrogen atom of the indenoindole derivative grows by hydrogen bonding have.

In addition, in the hybrid supported supported betalocene catalyst of the present invention, the first metallocene compound represented by Formula 1 and the second metallocene compound selected from the compounds represented by Formulas 3 to 5, By containing at least two metallocene compounds, it is possible to produce an olefin polymer which is a high molecular weight olefin-based copolymer having a high SCB content and has a wide molecular weight distribution at the same time as well as excellent physical properties as well as excellent processability.

In the process for producing a polyolefin according to the present invention, the co-catalyst to be supported on the carrier for activation of the first and second metallocene compounds is an organometallic compound containing a Group 13 metal, Is not particularly limited as long as it can be used in the polymerization of olefins.

According to an embodiment of the present invention, the cocatalyst to be used in each step may include at least one of an aluminum-containing primary catalyst of the following general formula (6) and a boron-containing secondary catalyst of the general formula (7)

[Chemical Formula 6]

_{- [Al (R 18) -O-} ] k -

In Formula (6), R ₁₈ is each independently halogen, halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,

(7)

T ⁺ [BG ₄ ] ^-

In Formula (7), T ⁺ is a polyatomic ion of +1 valence, B is boron of +3 oxidation state, and G is each independently selected from the group consisting of hydride group, dialkylamido group, halide group, alkoxide group, aryloxide group, Carbocyclic group, halocarbyl group, and halo-substituted hydrocarbyl group, wherein G has not more than 20 carbons, but G is a halide group in at least one position.

By using such first and second co-catalysts, the molecular weight distribution of the finally produced polyolefin becomes more uniform, and the polymerization activity can be improved.

The first cocatalyst of formula (6) may be an alkylaluminoxane compound having a linear, circular or network-like repeating unit bonded thereto. Specific examples of the first catalyst include methylaluminoxane (MAO), ethylaluminium Isobutylaluminoxane, butylaluminoxane, and the like.

Also, the second cocatalyst of formula (7) may be a tri-substituted ammonium salt, or a dialkylammonium salt, or a borate compound in the form of a trisubstituted phosphonium salt. Specific examples of the second cocatalyst include trimethylammonium tetraphenylborate, methyl dioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate , Methyltetradecyclooctadecylammonium tetraphenylborate, N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylanilinium (Tetrafluoroborate) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyl dioctadecylammonium tetrakis (Pentafluorophenyl) borate, triphenyl ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium (Pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (Pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis Tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate , Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) Borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6- Boronate in the form of a tri-substituted ammonium salt such as N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) compound; A borate-based compound in the form of a dialkylammonium salt such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) compound; (Pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, methyl dioctadecylphosphonium tetrakis ) Borate and the like, and the like.

In the mixed supported metallocene catalyst, the mass ratio of the total transition metal to the carrier included in the first metallocene compound represented by Formula 1 and the second metallocene compound represented by Formula 3 to 5 is 1:10 to 1: 1: 1,000. When the carrier and the metallocene compound are contained in the above mass ratio, they can exhibit an optimum shape.

In addition, the mass ratio of the cocatalyst compound to the carrier may be from 1: 1 to 1: 100. The mass ratio of the first metallocene compound represented by Formula 1 to the second metallocene compound represented by Formula 3 to 5 may be 10: 1 to 1:10, preferably 5: 1 to 1: 5. have. When the cocatalyst and the metallocene compound are contained in the mass ratio, the activity and the polymer microstructure can be optimized.

In the mixed supported metallocene catalyst, a carrier containing a hydroxy group on its surface may be used as the carrier. Preferably, the carrier contains a hydroxy group and a siloxane group having high reactivity, Can be used. Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. If the drying temperature of the carrier is less than 200 ° C, moisture is excessively large and the surface moisture reacts with the cocatalyst. When the temperature exceeds 800 ° C, the pores on the surface of the carrier are combined to reduce the surface area. And only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.

The amount of the hydroxy group on the surface of the carrier is preferably 0.1 to 10 mmol / g, more preferably 0.5 to 1 mmol / g. The amount of the hydroxyl group on the surface of the carrier can be controlled by the preparation method and conditions of the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than 0.1 mmol / g, the number of sites of reaction with the co-catalyst is small. If the amount is more than 10 mmol / g, the hydroxyl group may be present in the water other than the hydroxyl group present on the surface of the carrier particle. not.

In the preparation of the hybrid supported metallocene catalyst using the above-mentioned first and second metallocene compounds and the first and second co-catalysts or the like, it is preferable that the carrier is a mixture of a first metallocene compound and a first co- And then the second metallocene compound and the second co-catalyst are supported, but are not limited thereto. Between each of these carrying steps, a washing step using a solvent may be further carried out.

In the method for producing a polyolefin of the present invention, the first step of polymerizing the first olefin-based monomer is a step of polymerizing at least one first metallocene compound represented by the above-mentioned formula (1) Carried out in the presence of a hybrid supported metallocene catalyst comprising at least one second metallocene compound selected and a cocatalyst.

In the first step, any olefin-based monomer may be polymerized to prepare a polyolefin. Specific examples of the first olefin-based monomer that can be used at this time include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, Undecene, 1-undecene, 1-dodecene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene and 3-chloromethylstyrene. In one example of such a production method, ethylene is used to prepare polyethylene, or propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, , 1-heptene, 1-decene, 1-undecene or 1-dodecene may be copolymerized to prepare an ethylene-alpha olefin copolymer.

According to an embodiment of the present invention, the reaction mixture of the first step may contain at least one first metallocene compound represented by Formula 1, at least one second metallocene compound, a promoter compound, And a second step of polymerizing and polymerizing the second olefin-based monomer, the second hybrid supported metallocene catalyst containing the second olefin-based monomer, the molecular weight modifier, and the second olefin-based monomer.

Here, the second hybrid supported metallocene catalyst may be the same or different from the first hybrid supported metallocene catalyst. For example, when the types of the first and second hybrid supported metallocene catalysts are the same, problems of low productivity due to low mileage of the metallocene compound can be solved, and if necessary, polyolefins having a larger molecular weight Can be produced. When the types of the first and second hybrid supported metallocene catalysts are different, as described above, the physical properties of the produced polyolefin can be easily controlled, and a polyolefin having a wider multi-molecular weight distribution can be produced .

Here, the kind of the second olefin-based monomer may be the same as or different from that of the first olefin-based monomer, and may vary depending on the kind of the polyolefin to be obtained. According to one embodiment, the second olefinic monomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, -Decene, 1-undecene, 1-dodecene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene and 3-chloromethylstyrene.

Also, according to another embodiment, ethylene and a comonomer may be used together as the second olefin-based monomer; The comonomer may be selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl- At least one compound selected from the group consisting of styrene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene and 3-chloromethylstyrene.

The comonomer may be used in an amount of about 30 wt% or less, or 0 to about 20 wt%, or about 0.1 to 15 wt%, based on the ethylene content. When such a content of comonomer is copolymerized, the finally produced polyolefin can exhibit excellent mechanical properties and processability, particularly within a density range suitable for blow molding. However, when an excessively large amount of comonomer is used, the density of the polymer may be lowered and the bending strength may be lowered.

On the other hand, the molecular weight modifier introduced in the second step does not itself exhibit activity as an olefin polymerization catalyst, but it can be used to assist in the activity of the metallocene catalyst to enable the formation of a polyolefin having a larger molecular weight and a wider molecular weight distribution Lt; / RTI > Due to the action of the molecular weight modifier, even if most of the first metallocene compound is consumed in the first step, the polymerization of the olefin-based monomer can proceed effectively in the second step.

According to one embodiment, the molecular weight modifier may comprise a cyclopentadienyl metal compound of the formula 8 and a mixture of organoaluminum compounds of the formula 9, or a reaction product thereof.

[Chemical Formula 8]

Cp ⁶ Cp ⁷ M ⁴ X ' ₂

In Formula 8,

Cp ⁶ and Cp ⁷ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group or a ligand containing a substituted or unsubstituted fluorenyl group, M ⁴ is a Group 4 transition metal element , X 'is halogen;

[Chemical Formula 9]

R ^f R ^g R ^h Al

In the above formula (9)

R ^f , R ^g , and R ^h are each independently an alkyl group or a halogen having 4 to 20 carbon atoms, and R ^f , R ^g , and At least one of R ^h is an alkyl group having 4 to 20 carbon atoms.

Although the molecular weight modifier itself does not exhibit the activity as an olefin polymerization catalyst and the mechanism of its action is not specifically disclosed, it has been found that the production of a polyolefin having a larger molecular weight and a broad molecular weight distribution by assisting the activity of the metallocene catalyst .

Due to the action of such a molecular weight modifier, for example, in the case of producing a polyolefin in a multi-stage reactor to be described later, even if a large amount of metallocene catalyst is consumed in the reactor at the front stage, the high molecular weight polyolefin can be polymerized in the rear stage reactor, A polyolefin having a large molecular weight and a wide multi-branched molecular weight distribution can be produced.

According to one embodiment, the molecular weight modifier may be used in the form of a mixture in which the compounds of formulas (8) and (9) are not reacted with each other. Also, the molecular weight regulator may be prepared by reacting the reaction products of the compounds of the formulas (8) and (9), for example, the metal elements of these compounds, with one of X 'and / or R _d , R _e and R _f It can be used as an organometallic complex compound state. At this time, in addition to the organometallic complex, some unreacted compounds of the general formula (8) and / or the general formula (9) may be further included.

On the other hand, in the above molecular weight adjuster, specific examples of the cyclopentadienyl metal compound of the formula (8) include biscyclopentadienyl titanium dichloride, biscyclopentadienyl zirconium dichloride, biscyclopentadienyl hafnium dichloride, bis Nyltitanium dichloride, bis-fluorenyltitanium dichloride, and the like. Specific examples of the organoaluminum compound of formula (9) include triisobutylaluminum, trihexylaluminum, trioctylaluminum, diisobutylaluminum chloride, dihexylaluminum chloride, and isobutylaluminum dichloride.

The compound of formula (8) and the compound of formula (9) may be used in a molar ratio of about 1: 0.1 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 10 ^-7 to 10 ^-1 parts by weight, or about 10 ^-5 to 10 ^-2 parts by weight based on 100 parts by weight of the total of the first and second olefin-based monomers. When used in such a content range, the action and effect due to the addition of the molecular weight modifier can be optimized, and a polyolefin having excellent physical properties can be obtained.

Meanwhile, according to one embodiment of the present invention, the polymerization in the first step and the second step may be carried out by slurry polymerization in a hydrocarbon-based solvent (for example, an aliphatic hydrocarbon-based solvent such as hexane, butane, pentane, etc.) . As already described above, since the first and second metallocene compounds and the molecular weight modifier exhibit excellent solubility in an aliphatic hydrocarbon solvent, they are stably dissolved and supplied to the reaction system, Can be effectively performed.

The method of producing a polyolefin according to an embodiment of the present invention may be performed in a Cascade-CSTR reactor including first and second reactors. A schematic process using such a multi-stage CSTR reactor is as shown in FIG.

In this multi-stage CSTR reactor, the first step may be performed in the first reactor (R1), and the second step may be performed in the second reactor (R2). That is, in the first reactor (R1), the step of polymerizing the first olefin-based monomer (M1) is carried out in the presence of the first hybrid supported metallocene catalyst (C1). Then, the reaction mixture (slurry) in the first step is transferred to the second reactor R2 by a pressure difference. In the second reactor (R2), the second mixed supported metallocene catalyst (C2), the molecular weight modifier (MwE) and the second olefin monomer (M2) are further added to the reaction mixture in the first step A polymerization step is carried out.

In the first reactor R1, a low-molecular-weight polyolefin can be produced through a first-stage reaction, and a second-stage reaction in the second reactor R2 can produce a polyolefin having a higher molecular weight and a broad multi- Polyolefins can be prepared.

At this time, in the first reactor (R1), the polymerization may proceed in the presence of an inert gas such as nitrogen. The inert gas may act to maintain the reaction activity of the first metallocene compound for a long time by suppressing the abrupt reaction of the metallocene catalyst at the initial stage of the polymerization reaction. However, considering that the second metallocene compound is further added to the second reactor (R2), the amount of the inert gas used in the first reactor can be controlled.

In the first reactor (R1), hydrogen gas may be used for the purpose of controlling the molecular weight and the molecular weight distribution of the polyolefin in the first step reaction.

In the first step or the second step, an organoaluminum compound may be further added to remove moisture, oxygen, and the like in the reactor which can inhibit the activity of the catalyst compound. As a non-limiting example, the organoaluminum compound may be at least one compound selected from the group consisting of trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, aluminum dialkylhydride and alkylaluminum sesquihalide. More specifically, the organoaluminum compound is _{Al (C 2 H 5) 3} , Al (C 2 H 5) 2 H, Al (C 3 H 7) 3, Al (C 3 H 7) 2 H, Al (iC _{4 H 9) 2 H, Al} (C 8 H 17) 3, Al (C 12 H 25) 3, Al (C 2 H 5) (C 12 H 25) 2, Al (iC 4 H 9) (C 12 _{H 25) 2, Al (iC} 4 H 9) 2 H, Al (iC 4 H 9) 3, (C 2 H 5) 2 AlCl, (iC 3 H 9) 2 AlCl, (C 2 H 5) 3 Al ₂ Cl _3, and the like. These organoaluminum compounds can be continuously introduced into each reactor and can be introduced at a rate of about 0.1 to 10 moles per kg of reaction medium charged into each reactor for proper moisture removal.

On the other hand, in the first reactor in which the first step is carried out, the retention time of the raw material can be applied without particular limitation as long as it can form a polyolefin having a proper molecular weight distribution and density distribution. However, according to one embodiment, the residence time in the first reactor can be adjusted to about 1 to 5 hours. That is, if the residence time in the first reactor is shorter than 1 hour, the low molecular weight polyolefin may not be properly formed and the molecular weight distribution may be narrowed, thereby deteriorating the physical properties of the final polyolefin. On the contrary, if the residence time in the first reactor is excessively long, it is not preferable from the viewpoint of productivity.

The polymerization reaction temperature in the first step may be about 70 to 100 ° C. If the polymerization temperature is excessively low, it is not appropriate in view of the polymerization rate and productivity. Conversely, if the polymerization reaction temperature becomes higher than necessary, fouling may occur in the reactor.

In addition, the polymerization pressure of the first step may be about 5 to 10 bar to maintain a stable continuous process state.

The polymerization reaction in the first step may further include an organic solvent as a reaction medium or a diluent. Such an organic solvent may be used in an amount such that slurry phase polymerization or the like can be appropriately performed in consideration of the content of the first olefin-based monomer.

The polyolefin formed by the first stage polymerization reaction may be a low molecular weight polyolefin having a weight average molecular weight of about 50,000 to 200,000 g / mol, and may have a molecular weight distribution of about 5 to 100.

On the other hand, after the polymerization reaction of the first step as described above proceeds, the reaction mixture (slurry) of the first step is transferred to the second reactor and the polymerization reaction of the second step may be performed.

At this time, in the second step, in addition to the reaction mixture in the slurry transferred from the first reactor, the second hybrid supported metallocene catalyst, the molecular weight modifier, and the second olefin monomer are further charged, Whereby a high molecular weight polyolefin can be produced.

In the second reactor in which the second step is carried out, the residence time of the reactants can be applied without any particular limitation so long as it is capable of forming a polyolefin having an appropriate molecular weight distribution and density distribution. However, according to one embodiment, the residence time in the second reactor can be adjusted to about 1 to 3 hours. That is, if the residence time in the second reactor is shorter than 1 hour, the polyolefin having a high molecular weight may not be properly formed and the physical properties of the final polyolefin may be deteriorated. On the contrary, if the residence time in the second reactor becomes excessively long, it is not preferable from the viewpoint of productivity.

The polymerization reaction temperature in the second step may be about 70 to 100 ° C. If the polymerization temperature is excessively low, it is not appropriate in view of the polymerization rate and productivity. Conversely, if the polymerization reaction temperature becomes higher than necessary, fouling may occur in the reactor.

In addition, the polymerization pressure of the second step may be about 5 to 10 bar to maintain a stable continuous process state. However, it is preferable that the polymerization reaction pressure in the second step is adjusted to be about 0 to 3 bar lower than the pressure in the first step. That is, through this pressure difference, the reaction mixture on the slurry obtained through the first step can be smoothly transferred to the second reactor.

Further, in the polymerization reaction in the second step, an organic solvent may be further used as a reaction medium or a diluent, similarly to the polymerization reaction in the first step. Such an organic solvent may be used in an amount such that slurry phase polymerization or the like can be appropriately performed in consideration of the content of the second olefin-based monomer and the reaction mixture.

The polyolefin formed by the polymerization reaction in the second step may be a high molecular weight polyolefin having a weight average molecular weight of about 100,000 to 500,000 g / mol, and may have a molecular weight distribution of about 5 to 50. [

Meanwhile, according to one embodiment, the multi-stage CSTR reactor may further include a post reactor (Rp) for further polymerizing unreacted monomers in the slurry mixture delivered from the second reactor.

II . Polyolefin

Through such a series of polymerization reactions, a polyolefin having a large molecular weight and a wide multimolecular molecular weight distribution can be finally prepared.

That is, according to another embodiment of the present invention, there is provided a polyolefin prepared according to the above-described method and having a multimodal molecular weight distribution.

Such a polyolefin may have a large weight average molecular weight of about 100,000 to 500,000 g / mol by the action of the first and second metallocene compounds and the molecular weight regulator in the polymerization reaction of the above-described first and second steps, And may have a broader bimodal or multimodal molecular weight distribution.

Due to such a large molecular weight and a wide multimolecular molecular weight distribution, the polyolefin produced according to the method of one embodiment can simultaneously exhibit excellent mechanical properties and processability. Therefore, the polyolefin has a melt flow rate ratio (MFRR) value suitable for processing and is excellent in moldability, impact strength, tensile strength, ESCR and Full Notch Creep Test , FNCT) are excellent. In addition, the polyolefin is excellent in die swell characteristics, satisfies excellent mechanical properties and processability, and can be suitably applied as a polymer for blow molding.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

Synthetic example  1: 1st Metallocene  Synthesis of compounds

(1-a. Ligand  Preparation of compounds <

fluorene was dissolved in 5 mL of MTBE and 100 mL of hexane, and 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. (3.6 g) was dissolved in hexane (50 mL), and the fluorene-Li slurry was transferred for 30 minutes under a dry ice / acetone bath. The mixture was stirred overnight at room temperature. At the same time, 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole (12 mmol, 2.8 g) was dissolved in 60 mL of THF and 5.5 mL of 2.5 M n-BuLi hexane solution was dissolved in a dry ice / acetone bath And the mixture was stirred at room temperature overnight. dimethyl-5,10-dihydroindeno [1,2-b] indole-2-carboxylic acid was obtained by NMR spectroscopic analysis of the reaction solution of (6- (tert-butoxy) The Li solution was transferred under a dry ice / acetone bath. The mixture was stirred at room temperature overnight. After the reaction, the residue was extracted with ether / water, and the residual water of the organic layer was removed with MgSO ₄ to obtain a ligand compound (Mw = 597.90, 12 mmol). It was confirmed by 1H-NMR that two isomers were formed.

¹ H NMR (500 MHz, d 6 -benzene): -0.30 to -0.18 (3H, d), 0.40 (2H, m), 0.65-1.45 (8H, m), 1.12 D), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21 (1H, d), 4.34-4.38

(1-b. Preparation of metallocene compound)

7.2 g (12 mmol) of the ligand compound synthesized in 1-a above was dissolved in 50 mL of diethylether, and 11.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. And dried in vacuo to obtain a brown color sticky oil. And dissolved in toluene to obtain a slurry. ZrCl ₄ (THF) ₂ was prepared and 50 mL of toluene was added thereto to prepare a slurry. A 50 mL toluene slurry of ZrCl ₄ (THF) ₂ was transferred in a dry ice / acetone bath. It was changed to violet color by stirring overnight at room temperature. The reaction solution was filtered to remove LiCl. Toluene in the filtrate was removed by vacuum drying, and then hexane was added thereto for sonication for 1 hour. The slurry was filtered to give 6 g of dark violet metallocene compound (Mw 758.02, 7.92 mmol, yield 66 mol%), which was a filtered solid. Two isomers were observed in < 1 > H-NMR.

¹ H NMR (500 MHz, CDCl ₃ ): 1.19 (9H, d), 1.71 (3H, d), 1.50-1.70 (4H, m), 1.79 (2H, m), 3.91 (3H, d), 6.66-7.88 (15H, m)

Synthetic example  2: 1st Metallocene  Synthesis of compounds

(2-a. Ligand  Preparation of compounds <

Add 2.63 g (12 mmol) of 5-methyl-5,10-dihydroindeno [1,2-b] indole to a 250 mL flask and dissolve in 50 mL of THF. Add 6 mL of 2.5 M n-BuLi hexane solution to the dr yice / acetone bath And the mixture was stirred at room temperature overnight. In another 250 mL flask, 1.62 g (6 mmol) of (6- (tert-butoxy) hexyl) dichloro (methyl) silane was dissolved in 100 mL of hexane, and then 5-methyl-5,10-dihydroindeno [1,2-b] indole in tetrahydrofuran and slowly stirred at room temperature overnight. After the reaction, the residue was extracted with ether / water. The residual water in the organic layer was removed with MgSO ₄ and vacuum dried to obtain 3.82 g (6 mmol) of a ligand compound.

^{1 H NMR (500 MHz, CDCl3} ): -0.33 (3H, m), 0.86 ~ 1.53 (10H, m), 1.16 (9H, d), 3.18 (2H, m), 4.07 (3H, d), 4.12 ( 3H, d), 4.17 (1 H, d), 4.25 (1 H, d), 6.95-7.92 (16 H, m)

(2-b. Metallocene  Preparation of compounds <

After dissolving 3.82 g (6 mmol) of the ligand compound synthesized in 2-a above in 100 mL of toluene and 5 mL of MTBE, 5.6 mL (14 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dryice / acetone bath, Lt; / RTI > 2.26 g (6 mmol) of ZrCl ₄ (THF) ₂ was added to another flask and 100 ml of toluene was added to prepare a slurry. The toluene slurry of ZrCl ₄ (THF) ₂ was transferred to the litigated ligand in a dry ice / acetone bath. It was stirred overnight at room temperature and changed to violet color. The reaction solution was filtered to remove LiCl, and the resulting filtrate was vacuum-dried, and hexane was added thereto for sonication. The slurry was filtered to obtain 3.40 g (yield: 71.1 mol%) of a metallocene compound of dark violet filtered solid.

^{1 H NMR (500 MHz, CDCl3} ): 1.74 (3H, d), 0.85 ~ 2.33 (10H, m), 1.29 (9H, d), 3.87 (3H, s), 3.92 (3H, s), 3.36 (2H , < / RTI > m), 6.48 to 8.10 (16H, m)

Synthetic example  3: 2nd Metallocene  Synthesis of compounds

(CH ₂ ) ₆ -Cl was prepared by the method described in Tetrahedron Lett. 2951 (1988) using 6-chlorohexanol, which was reacted with NaCp t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ (yield 60%, bp 80 ° C / 0.1 mmHg).

Further, t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 ° C, and then normal butyl lithium (n-BuLi) was slowly added thereto. . The solution was again slowly added at -78 ° C to a suspension of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol) / THF (30 mL) in a suspension solution and slowly added at room temperature The reaction was further continued for 6 hours.

All volatile materials were vacuum dried, and hexane solvent was added to the obtained oily liquid substance to be filtered. The filtered solution was vacuum dried, and hexane was added thereto to induce a precipitate at a low temperature (-20 ° C). The white solid precipitate was filtered out at a low temperature _{[tBu-O- (CH 2)} 6 -C 5 H 4] 2 ZrCl 2 (Yield: 92%).

^{1 H NMR (300 MHz, CDCl} 3): 6.28 (t, J = 2.6 Hz, 2 H), 6.19 (t, J = 2.6 Hz, 2 H), 3.31 (t, 6.6 Hz, 2 H), 2.62 ( t, J = 8 Hz), 1.7-1.3 (m, 8 H), 1.17 (s, 9 H).

_{^{13 C NMR (CDCl 3):}} 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

Manufacturing example  1: hybrid bearing Metallocene  Preparation of Catalyst

Silica (SYLOPOL 948, Grace Davison) was dehydrated under vacuum at a temperature of 400 ° C for 15 hours.

Add 10 g of dried silica to a glass reactor, add 100 mL of toluene and stir. 50 mL of 10 wt% methylaluminoxane (MAO) / toluene solution was added, and the mixture was slowly reacted at 40 ° C with stirring. Thereafter, the reaction product was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed by decompression. After 100 mL of toluene was again added, 0.25 mmol of the first metallocene compound according to Synthesis Example 2 was dissolved in toluene and the mixture was reacted for 1 hour. After the reaction was completed, 0.25 mmol of the first metallocene compound according to Synthesis Example 1 was dissolved in toluene, and the reaction was further continued for 1 hour. Finally, 0.25 mmol of the second metallocene compound according to Synthesis Example 3 was dissolved in toluene, and the reaction was further performed for 1 hour. After the reaction was completed, stirring was stopped and the toluene layer was separated and removed. 1.0 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) was added thereto and stirred for 1 hour. Toluene was removed to prepare a hybrid supported catalyst.

Manufacturing example  2: Preparation of molecular weight regulator

1.25 g of bis (cyclopentadienyl) titanium dichloride and 10 ml of toluene were sequentially added to a 250-ml round bottom flask and stirred. To this was added 10 ml of triisooctylaluminum (1M in hexane), stirred at room temperature for 3 days, and then the solvent was removed in vacuo to give a green mixture, which was either oxidized or colored Did not change. Hereinafter, the green mixture was used without purification. Also, it was confirmed by 1 H NMR that the mixture was bis (cyclopentadienyl) octyl titanium and dioctylaluminium chloride.

¹ H NMR (CDCl ₃ , 500 MHz): 7.31 (br s, 10H), 2.43 (d, 4H), 1.95-1.2

Example  One: Polyolefin  Produce

A multi-stage continuous CSTR reactor composed of two 0.2 m ³ capacity reactors as shown in Fig. 1 was prepared.

Was fed into the first reactor R1 at a flow rate of 23 kg / hr of hexane, 7 kg / hr of ethylene, 2.0 g / hr of hydrogen, and 30 mmol / hr of triethylaluminum (TEAL) The metallocene catalyst was injected at 2 g / hr (170 μmol / hr). At this time, the first reactor was maintained at 80 ° C, the pressure was maintained at 8 bar, the residence time of the reactant was maintained at 2.5 hours, and the slurry mixture containing the polymer was continuously supplied to the second reactor I would like to move on.

Was injected into the second reactor R2 at a flow rate of 25 kg / hr of hexane, 6 kg / hr of ethylene, 15 cc / min of 1-butene and 30 mmol / hr of triethylaluminum (TEAL) A metallocene catalyst of 2 g / hr (170 μmol / hr) and a molecular weight modifier (MwE) according to Preparation Example 2 were injected at 34 μmol / hr. The second reactor was maintained at 78 占 폚, the pressure was maintained at 6 bar, the residence time of the reactant was maintained at 1.5 hours, and the polymer mixture was continuously passed through a post reactor while maintaining a constant liquid level in the reactor. Respectively.

The post reactor was maintained at 75 DEG C and unreacted monomers were polymerized. The polymerization product was then made into the final polyethylene via a solvent removal unit and dryer. The prepared polyethylene was mixed with 1000 ppm of calcium stearate (manufactured by DuPont) and 2000 ppm of heat stabilizer 21B (manufactured by Songwon Industrial Co., Ltd.) and then made into pellets.

Example  2: Polyolefin  Produce

The procedure of Example 1 was repeated except that the amount of the mixed supported metallocene catalyst according to Production Example 1 injected into the second reactor (R2) was adjusted to 4 g / hr (340 μmol / hr) Respectively.

Comparative Example  One: Polyolefin  Produce

The polyethylene was prepared in the same manner as in Example 1, except that the mixed supported metallocene catalyst according to Production Example 1 was not injected in the second reactor (R2).

Test Example

The properties of the polyethylene prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

1) Molecular weight distribution (PDI): The weight average molecular weight was determined by gel permeation chromatography (GPC) divided by the number average molecular weight.

2) Melt Index (MI): Measured according to ASTM D1238 under a temperature of 190 ° C and a load of 21.6 kg.

3) Stress cracking resistance (FNCT): Measured according to ISO 16770 at a temperature of 80 캜 and a pressure of 4.0 MPa.

Catalyst feed rate MwE
(mole / mole of metal) MI PDI FNCT
(hr) R1 R2 Example 1 One One 0.2 6.2 16 290 Example 2 One 2 0.2 4.7 20 340 Comparative Example 1 One 0 0.2 6.7 16 290

Referring to Table 1, in Examples 1 and 2 in which olefin polymerization was carried out by additionally feeding a mixed supported metallocene catalyst together with a molecular weight regulator to the second reactor (R2), the melt index And molecular weight distribution, but showed high stress cracking resistance.

R1: first reactor
R2: the second reactor
Rp: Post reactor
C1: First hybrid supported metallocene catalyst
C2: Second hybrid supported metallocene catalyst
M1: the first olefin monomer
M2: the second olefin monomer
MwE: molecular weight regulator

Claims (12)

In the presence of a first mixed metallocene catalyst comprising at least one first metallocene compound, at least one second metallocene compound, a co-catalyst compound, and a carrier, the first olefinic monomer- Stage 1; And
A second mixed supported metallocene catalyst comprising at least one of the first metallocene compound, at least one second metallocene compound, a co-catalyst compound, and a carrier in the reaction mixture of the first step, And a second step of further polymerizing and polymerizing a second olefin-based monomer;
Wherein the first metallocene compound is a compound of one of the following structural formulas,

;
Wherein the second metallocene compound is a compound represented by the following formula (3), respectively:
(3)
(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹³ _-n
In Formula 3,
M ¹ is a Group 4 transition metal;
Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^a and R ^b are the same or different and are each independently selected from the group consisting of hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 C20 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z ¹ represents a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
n is 1 or 0;
The method according to claim 1,
Wherein the first hybrid supported metallocene catalyst and the second hybrid supported metallocene catalyst are the same or different catalysts.
delete delete The method according to claim 1,
Wherein the co-catalyst comprises at least one compound selected from the group consisting of an aluminum-containing primary co-catalyst of the following formula (6) and a boron-containing secondary catalyst of the following formula (7)
[Chemical Formula 6]
_{- [Al (R 18) -O-} ] k -
In Formula (6), R ₁₈ is each independently halogen, halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,
(7)
T ⁺ [BG ₄ ] ^-
In Formula (7), T ⁺ is a polyatomic ion of +1 valence, B is boron of +3 oxidation state, and G is each independently selected from the group consisting of hydride group, dialkylamido group, halide group, alkoxide group, aryloxide group, Carbocyclic group, halocarbyl group, and halo-substituted hydrocarbyl group, wherein G has not more than 20 carbons, but G is a halide group in at least one position.
The method according to claim 1,
Wherein said carrier is selected from the group consisting of silica, silica-alumina and silica-magnesia.
The method according to claim 1,
Wherein the molecular weight modifier is a cyclopentadienyl metal compound represented by the following formula (8), a mixture of an organoaluminum compound represented by the following formula (9), or a reaction product thereof:
[Chemical Formula 8]
Cp ⁶ Cp ⁷ M ⁴ X ' ₂
In Formula 8,
Cp ⁶ and Cp ⁷ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group or a ligand containing a substituted or unsubstituted fluorenyl group, M ⁴ is a Group 4 transition metal element , X 'is halogen;
[Chemical Formula 9]
R ^f R ^g R ^h Al
In the above formula (9)
R ^f , R ^g , and R ^h are each independently an alkyl group or a halogen having 4 to 20 carbon atoms, and R ^f , R ^g , and At least one of R ^h is an alkyl group having 4 to 20 carbon atoms.
The method according to claim 1,
The first olefin-based monomer is at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, A method for producing a polyolefin comprising at least one compound selected from the group consisting of styrene, 1-dodecene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene and 3-chloromethylstyrene.
The method according to claim 1,
Wherein the second olefin-based monomer is selected from the group consisting of ethylene; Hexene, 1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, And at least one comonomer selected from the group consisting of ethylene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene and 3-chloromethylstyrene.
The method according to claim 1,
Wherein the polymerization in the first step and the second step proceeds in a slurry-phase polymerization in a hydrocarbon-based solvent.
The method according to claim 1,
A process for preparing a polyolefin in a Cascade-CSTR reactor.
The method according to claim 1,
The first step is carried out in a first reactor,
Wherein the second step is carried out in a second reactor,
Wherein the second mixed supported metallocene catalyst and the second olefin based monomer are further added to the reaction mixture delivered from the first reactor in the second reactor.

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