WO2016186295A1

WO2016186295A1 - Supported hybrid catalyst system, and method for preparing polyolefin by using same

Info

Publication number: WO2016186295A1
Application number: PCT/KR2016/000880
Authority: WO
Inventors: 이승미; 이용호; 박진영; 이기수; 신은지; 사석필
Original assignee: 주식회사 엘지화학
Priority date: 2015-05-15
Filing date: 2016-01-27
Publication date: 2016-11-24

Abstract

The present invention relates to a supported hybrid catalyst system, and a method for preparing a polyolefin by using the same. According to the present invention, the supported hybrid catalyst system can simultaneously carry out oligomerization and polymerization of olefin monomers with high efficiency in a single reactor without separately carrying out a process for preparing α-olefins. Therefore, production costs of a final product can be lowered since the cost of preparing or purchasing a comonomer, which is an expensive material, is reduced.

Description

【Specification】

[Name of invention]

Common supported catalyst system and method for producing polyolefin using the same

Technical Field

Mutual citation with the related application (s)

This application is filed with Korean Patent Application No. 10-2015-0068299 filed May 15, 2015, Korean Patent Application No. 10-2015-0068300 filed May 15, 2015, and Korean Patent Application No. 10-2016 filed January 26, 2016. Claiming the benefit of priority based on -0009561, all contents disclosed in the literature of the corresponding Korean patent applications are incorporated as part of this specification. The present invention relates to a supported catalyst system and a method for producing a polyolefin using the same.

Background Art

Linear alpha-efin is an important material used in comonomers, cleaners, lubricants, plasticizers, etc. It is widely used commercially, especially 1-nuxene and 1-octene in the production of linear low density polyethylene (LLDPE) It is often used as a comonomer to control the density of

Conventional manufacturing process of LLDPE (Linear Low-Density Polyethylene) is used to form a branch in the polymer backbone with ethylene to control density. For example, co-polymerization with comonomers such as 1-nuxene and 1-octene was performed.

Therefore, for the production of LLDPE having a high content of comonomers, there is a problem that the price of comonomers occupies a large part of the manufacturing cost. In order to solve these problems, various methods have been tried.

In addition, since alpha-olefins have different types of market and market size, the technology for selectively producing a specific olefin is important commercially. Recently, ethylene igomerization or 1-nucleene or ethylene oligomerization is used. Much research is being done on chrome catalyst technology to produce 1-octene with high selectivity. Conventional commercial manufacturing methods for producing 1-nuxene or 1-octene include SHOP process of Shell Chemical and Ziegler Process of Chevron Philips. It is possible to produce a wide range of alpha-olefins with C4-C20 carbon atoms. However, the above method synthesizes alpha-olefins of various lengths simultaneously according to the Schultz-Flory distribution. There was a need to go through the separation process.

In order to solve this problem, a method of selectively synthesizing 1-nucleene through ethylene trimerization reaction or selectively synthesizing 1-octene through ethylene tetramerization reaction has been proposed. Much research is being done on catalyst systems that enable oligomerization.

However, even in the case of a catalyst system capable of oligomerization of such selective ethylene, the process is performed by separating alpha-lephine produced by the mercury reaction and adding it as a comonomer to the copolymerization process with ethylene. As a result, the process is cumbersome and the production cost is high.

Contents of the Invention

[Task to be solved]

Accordingly, an object of the present invention is to provide a catalyst system capable of simultaneously performing oligomerization and copolymerization of olefin monomers in a single reactor with high efficiency and a method of preparing polyolefin using the same without the need to perform a separate process for preparing alpha-olefins. It is.

[Measures to solve the problem]

According to one aspect of the present invention,

At least two groups represented by the following formula (1) in the molecule, at least one of the groups represented by the formula (1) is a chromium (Cr) coordination bond to the atom (P),

A group (L) which connects each of the two or more groups with 4 to 8 carbon atoms, respectively, an aliphatic group having 2 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, an alicyclic group having 2 to 20 carbon atoms, and carbon atoms Heteroaliphatic group of 2 to 20, or the aliphatic group, heteroaliphatic group, alicyclic group, And at least one organic cream compound having a group having two or more heteroalicyclic groups bound thereto; and

Provided is a common supported catalyst system in which at least one metallocene compound is supported on a carrier.

[ One]

In Formula 1,

^* Is a site that binds to the group (L) connecting between the two or more groups,

R! R ₄ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl alkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, or 7 to 20 carbon atoms. It is a 20 alkoxy aryl group. In addition, according to another aspect of the present invention provides a method for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the common supported catalyst system.

【Effects of the Invention】

By using the common supported catalyst system according to the present invention, the elimination and copolymerization of the olephine monomers can be carried out at the same time with high efficiency in a single reaction vessel without the need to perform a separate process for producing the alpha-olefin. The cost of manufacturing or purchasing the comonomer, a raw material, can be reduced, resulting in lower production costs for the final product.

The alpha-olefin comonomers produced primarily in the common supported catalyst system of the present invention are present in the supported catalyst system or in a short distance from the supported catalyst system, thereby increasing the accessibility of the metallocene compound as a (co) polymerization catalyst. High conversion rate has improved co-polymerization efficiency.

In addition, since there are few comonomers that are not incorporated into polyolefins in the polymerization process, the fouling caused by this is reduced. Stability can be increased, and high-quality linear low density polyethylene can be produced by increasing the content of SCB (short chain branch) and LCB (long chain branch) in polyolefin without additional comonomer.

[Specific details for carrying out the invention]

The invention is explained in more detail in the following Examples. However, the following Examples are merely to illustrate the present invention, and the contents of the present invention are not limited to the following Examples.

Unless expressly stated throughout this specification, the terminology is merely for referring to specific embodiments and is not intended to limit the invention. As used herein, the singular forms “a”, “an” and “the” include plural forms as well, unless the phrases clearly indicate the opposite. In addition, the meaning of "include" as used in the specification embodies specific characteristics, domain constants, steps, actions, elements and / or components, and other specific characteristics, domains, integers, steps, operations, elements, components and / or groups. It does not exclude the presence or addition of.

Hereinafter, a description will be given in more detail about a supported catalyst system according to a specific embodiment of the present invention, and a method for preparing polyolefin using the same. According to one embodiment of the present invention,

As a group (L) connecting each of the two or more groups with 4 to 8 carbon atoms, each of an aliphatic group having 2 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, an alicyclic group having 2 to 20 carbon atoms, At least one organic chromium compound having a heterocyclic group of 2 to 20 carbon atoms, or a group in which two or more kinds of the aliphatic group, heteroaliphatic group, alicyclic group, and heteroalicyclic group are bonded; and

At least one metallocene compound is supported on a carrier supported catalyst system.

to provide.

[Formula 1] F 3

In Chemical Formula 1,

* Is a site that binds to the group (L) connecting between the two or more groups,

Ri to R ₄ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl alkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, or 7 carbon atoms To alkoxyaryl group of 20. In the present specification, the term 'common supported catalyst system' refers to an organic cream compound metallocene compound and a carrier; or alternatively, an organic cream compound, a metallocene compound, a cocatalyst and a carrier are added at the same time or in any order, thereby increasing activity. The catalyst supported catalyst system can be added to the reaction system in the presence or absence of solvent and monomers.

In addition, the term "oligomerization" used in the present invention means that the olefinic monomer is polymerized. Depending on the number of olefinic monomers to be polymerized, it is called trimerization and tetramerization, which are collectively referred to as multimerization or oligomerization. In particular, oligomerization in the present invention means, but is not limited to, the selective preparation of 1-nuxene and / or 1-octene which are the main comonomers of LLDPE from ethylene.

This selective olefin oligomerization reaction is closely related to the catalyst system used. The catalyst used for lepin oligomerization reaction includes a ligand and a transition metal coordinating to the ligand, wherein As a result, the structure of the active catalyst may be changed, and thus, the selectivity and activity of the alpha-olefin may be different.

The organic chromium compound according to the embodiment of the present invention includes a ligand compound which is not previously known, and by appropriately adjusting the substituent introduced into the ligand compound, it is possible to easily control the electronic and three-dimensional environment around the transition metal (Cr). It was confirmed that oligomerization of olefins was possible with high catalytic activity and selectivity.

Organic chromium compound according to an embodiment of the present invention, in the molecule

One or more diphosphinoamine functional groups (hereinafter referred to as PNP functional groups) represented by 1, and one or more of these PNP functional groups contain a complex compound in which a cr (Cr) coordination bond to a factor (P) That is, the organochrome compound according to one embodiment of the present invention is a compound in which chromium forms a coordinating bond to any one or more PNP functional groups in a ligand compound including two or more PNP functional groups in a molecule.

Such organic cream compounds may serve to perform oligomerization of olefinic monomers with excellent catalytic activity in the supported catalyst system of the present invention.

[ One]

In Chemical Formula 1

Ri to R ₄ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl alkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, or 7 carbon atoms To alkoxyaryl group of 20. More specifically, specific examples of the ligand compound including one or more PNP functional groups represented by the following Chemical Formula 1 include the following compounds, but the present invention is not limited thereto.

The ligand compound may be synthesized in the same manner as in the following reaction formula 1, but the present invention is not limited thereto. The method for preparing the ligand compound will be described in more detail than in the following Examples.

[Banungsik 1]

In the reaction form 1,

The definitions of Ri to R ₄ and L are the same as those defined in Formula 1 above, and X is halogen.

In addition, the specific ligand compound may include all possible optical isomers.

The organochrome compound of the present invention may be a chromium complex compound obtained by reacting the ligand compound with a chromium source.

Specific examples of the chromium source forming the ligand compound with the ligand compound include chloroacetate, acetylacetonate, chromium trichloride tristetrahydrofuran, chromium (lll) -2-ethylnucleoacetate, chromium Tris (2,2,6,6-tetramethyl-3,5-heptanedionate),

Chromium may be one or more selected from the group consisting of benzoylacetonate, crumb (III) nucleofluoro-2,4-pentanedionate and crumb (NI) acetate hydroxide.

The PNP functional group of Formula 1 is connected to 4 to 8 carbon atoms, and the group (L) connecting the PNP functional group is an aliphatic group having 2 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, and having 2 to 20 carbon atoms. Alicyclic group, heterocyclic group having 2 to 20 carbon atoms, or the aliphatic group, heteroaliphatic group, cycloaliphatic group, and heteroalicyclic group. Due to these structural features, the ligand compound and the transition metal ( The organic cream compound, which is a complex of Cr) coordination complex, interacts easily with PNP-Cr depending on the electronic and three-dimensional environment around the transition metal, showing high oligomerization activity, and especially for 1-nuxene and 1-octene. High selectivity can be indicated.

Therefore, the organic chromium compound may be applied to a common supported catalyst system to exhibit high oligomerization reaction activity, and in particular, may exhibit high selectivity for 1-nuxene, 1-octene and the like. Therefore, 1-nucleene, 1-octene, etc. produced therefrom High quality polyolefin can be produced by incorporation into high efficiency comonomer from polyolefin polymerization reaction.

In the definition of the above formula, the aryl group is preferably an aromatic ring having 6 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like. It doesn't work.

And, an alkylaryl group means a C6-C20 aryl group in which one or more linear or branched alkyl groups are substituted, and the arylalkyl group means a straight-chain or branched alkyl group in which one or more C6-C20 aryl groups are substituted at least one. The alkoxy aryl group means an aryl group having 6 to 20 carbon atoms in which at least one alkoxy group is substituted.

In addition, a hetero element means N, 0, F, S, P, and a heteroaryl group means an aryl group containing one or more hetero elements.

Halogen also means fluorine (F), chlorine (CI), brine (Br), and iodine.

On the other hand, the organic chromium compound of one embodiment of the present invention includes two or more, preferably two groups represented by the formula (1), these are groups (L) connecting 4 to 8 carbon atoms, 2 to An aliphatic group of 20, a heteroaliphatic group of 2 to 20 carbon atoms, an alicyclic group of 2 to 20 carbon atoms, a heteroalicyclic group of 2 to 20 carbon atoms, or the aliphatic group, a heteroaliphatic group, an alicyclic group, and a heteroalicyclic group Groups can be linked to two or more combined groups. ^'

Specific examples of these linking groups (ᅵ) are as follows:

In the above formulas, * is a moiety bonded to N in Formula 1, R 'is independently hydrogen or alkyl of 1 to 5 carbon atoms, p is an integer of 1 to 6, q is an integer of 1 to 5 A plurality of R's bonded to one ring (cyclonucleic acid or phenyl) may be the same or different from each other.

As such, when two groups represented by Chemical Formula 1 are connected by 4 to 8 carbon atoms, the groups connecting by 4 to 8 carbon atoms may be mutually connected to each other. It is desirable to include flexible aliphatic groups for smooth operation.

That is, even if two groups represented by the formula (1) are connected with 4 to 8 carbon atoms, they do not include aliphatic groups as in the case where the formula (1) is substituted at positions 1 and 4 of the cyclohexane (cydohexane) When linked, including only cycloaliphatic or aromatic groups, the interactions are extremely limited, resulting in significantly lower activity per unit PNP-Cr, and selection for low carbon number alpha-lepine such as 1-nuxene and 1-octene. Can also be reduced.

The organic cream compound including the group represented by Formula 1 may be a catalyst precursor capable of performing oligomerization reaction of an olefin by coordinating a PNP functional group with chromium. As described above, the organochromium compound of the above embodiment forms at least one PNP functional group at a suitable position, thereby forming a crack complex, and thus, an example will be described later to increase catalyst activity and selectivity resulting from the interaction between the two groups. It was confirmed at.

According to an embodiment of the present invention, Formulas 1 to R4 may be the same as each other, preferably phenyl.

On the other hand, according to one embodiment of the present invention, when the organic chromium compound includes two groups represented by the formula (1), both of the groups represented by the formula (1) is a coordination bond in the two groups represented by the formula (1) It can be represented as 1-1:

In Chemical Formula 1-1, L and R! To R ₄ is as defined in Formula 1, ^ to Y ₃ are each independently halogen, hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or a heterohydrocarbyl group having 1 to 10 carbon atoms.

That is, L is a group connecting 4 to 8 carbon atoms between nitrogen (Ν) atoms, an aliphatic group of 2 to 20 carbon atoms, a heteroaliphatic group of 2 to 20 carbon atoms, an alicyclic group of 2 to 20 carbon atoms, carbon number 2 to 20 heteroalicyclic group, or the aliphatic group, heteroaliphatic group, alicyclic group, and heteroalicyclic group is a group of two or more bonded,

Ri to F are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl alkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, or 7 to 20 carbon atoms 20 alkoxyaryl groups;

Υι to Υ ₃ are each independently halogen, hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or a heterohydrocarbyl group having 1 to 10 carbon atoms.

According to an embodiment of the present invention, Formula 1-1 to R ₄ may be the same as each other, preferably phenyl.

In addition, Y ₂ and Y ₃ of Formula 1-1 may each independently be a halogen, hydrogen, hydrocarbyl group or heterohydrocarbyl group.

Υι, Υ ₂ and 丫 3 are each independently an acetylacetonate group (cetylacetone), an acetate group (acetate), a tetrahydrofuran group (tetrahydrofuran), 2-ethyl hexanoate group (2-ethyl hexanonate), butyrate group butyrate, pentanoate, laurate, or stearate.

In addition, the specific organochromium compound may include all possible optical isomers. Meanwhile, according to another embodiment of the present invention, the organic chromium compound includes two groups represented by Chemical Formula 1, and only one of two groups represented by Chemical Formula 1 forms a coordination bond. If present, it may be represented by Formula 1-2:

[

In Chemical Formulas 1 to 2, L, R! To F ^ Y, and Y ₃ are as defined in Chemical Formula 1-1.

That is, the organic chromium compound of the present invention may be one of the ligand group of Formula 1 is formed with the coordination bond and the remaining part of the free ligand (free Ngand) without forming the coordination bond with the creme.

As such, the PNP functional group that forms a coordinative bond with chromium exhibits an oligomerization activity with respect to the olepin-based monomer, but the phosphorus (P) atom portion of the free glass coordination bond does not form a carrier or cocatalyst in the common supported catalyst system. Thus, Lewis acid-base bonds can be achieved. Therefore, the supporting capacity of the PNP-Cr catalyst can be enhanced to increase the supporting efficiency and thus the activity of the supported catalyst system and the efficiency of the limerization process. Can be higher than

An organochromium compound including a free ligand, such as Formula 1-2, may be obtained by reacting a molar number of crack source less than the number of moles of PNP functional groups present in the ligand compound of Formula 1. For example, less than 1 mole, for example, about 0.2 to about 0.8 mole, preferably about 0.4 to about 0.6 mole of chromium source, per 1 mole of the PNP functional group present in the ligand compound represented by Formula 1 Organic cream compounds with at least some free glass can be produced. It may be desirable to include chromium sources in this range in terms of achieving both catalytic activity and supporting efficiency improvements simultaneously.

On the other hand, the common supported catalyst system of the present invention is at least one metallocene compound Include.

Alpha-olefin comonomers such as 1-nuxene or 1-octene produced by oligomerization of the olefinic monomers by the organic chromium compound are catalyzed by the metallocene compound supported on the supported catalyst system of the present invention. Copolymerizes with other olefinic monomers to produce polyolefins. At this time, the alpha-olefin comonomers produced first by the organic cream compound are present in the supported catalyst system or in a short distance from the supported catalyst system, and thus have high accessibility with the metallocene compound which is a polyolefin (co) polymer catalyst. High comonomer conversion rates. In addition, due to the high accessibility to the metallocene compound as described above, there are few comonomers which are not incorporated into the polyolefin in the copolymerization process, thereby reducing the fouling caused by the process, thereby increasing process stability. It is possible to produce high quality linear low density polyethylene because the content of SCB (short chain branch) and LCB (long chain branch) in polyolefin can be increased without the addition of expensive comonomer.

According to an embodiment of the present invention, the metallocene compound may be at least one selected from the compounds represented by the following Chemical Formulas 3 to 6:

[Formula 3]

(Cp R ^a ) _n (Cp ² R ^b ) MZ _3- n

In Formula 3,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and 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 hydrocarbons of 1 to 20 carbon atoms;

R ^a and R ^b are the same or different and are 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 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 as or different from each other, and are each independently 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;

R ^c and R ^d are the same or different and are 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 ² is a halogen atom, C 1 to C 20 alkyl, C 2 to C 10 alkenyl, C 7 to C 40 alkylaryl, C 7 to C 40 arylalkyl, C 6 to C 20 aryl, substituted or unsubstituted C 1 to C 20 alkylidene 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 Cp ³ R ^c ring and the Cp ⁴ R ^d ring or crosslinks one Cp ⁴ R ^d ring with M ² Or a combination thereof;

m is 1 or 0;

[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-l-indenyl and fluorenyl radicals, which can be substituted with 1 to 20 hydrocarbons 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 C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ³ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 aryl ^' alkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkyl A lidene, a substituted or unsubstituted amino group, C 2 to C 20 alkylalkoxy, or C 7 to C 40 arylalkoxy;

B ² is at least one of carbon, germanium, silicon, phosphorus or nitrogen atom-containing radicals or a combination thereof that crosslinks the Cp ⁵ R ^e ring and J;

J is any one selected from the group consisting of NR ^f , O, 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 An alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a 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 each independently hydrogen, halogen, alkyl group of C1 to C20 A C2 to C20 alkenyl group, or a C6 to C20 aryl group;

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

B ³ 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

An alkyl group of C20, an alkenyl group of C2 to C20, an aryl group of C6 to C20, a nitro group, an amido group, an alkylsilyl group of C1 to C20, an alkoxy group of C1 to C20, or a sulfonate group of C1 to C20;

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

In Formulas 7a, 7b and 7c R9 to R25 and R9 'to R17' 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 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 adjacent to R18 to R25 The foregoing can be linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

On the other hand, in the metallocene compound of Formula 6, it will be described in more detail with respect to each substituent.

The C1 to C20 alkyl group includes a linear or branched alkyl group, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nuclear group, heptyl group, jade Tilts, etc., but this is not limited. The alkenyl group of C2 to C20 includes a straight or branched alkenyl group, and specifically, may include an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like, but is not limited thereto.

The C6 to C20 aryl group includes a monocyclic or condensed aryl group, and specifically includes a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but is not limited thereto.

The C5 to C20 heteroaryl group includes a monocyclic or condensed ring heteroaryl group, carbazolyl group, pyridyl group, quinoline group, isoquinoline group, thiophenyl group, furanyl group, imidazole group, oxazolyl group, thiazolyl group , Triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.

Examples of the alkoxy group for C1 to C20 include a hydroxy group, a special group, a phenyloxy group, and a cyclonuclear oxy group, but are not limited thereto.

The Group 4 transition metals include, but are not limited to, titanium, zirconium, and hafnium.

In Formulas 7a, 7b, and 7c, which are ligand-derived structures included in Formula 6, R9 to R25 and R9 'to R17' are each independently hydrogen, methyl, ethyl, propyl, isopropyl, or n-butyl. Group, tert-butyl group, pentyl group, nuclear group, heptyl group, It is more preferable that they are octyl, phenyl, halogen, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, hydroxy or ethoxy. It is not definite.

In addition, E of Formula 6 is more preferably a straight chain or branched alkylene group of C4 to C8, but is not limited thereto. In addition, the alkylene group is an alkyl group of C1 to C20, an alkenyl group of C2 to C20, Or an aryl group of C6 to C20.

In addition, A in Formula 6 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert- butylmethyl group, 1- ethoxyethyl group, 1-methyl It is preferable that the -1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group is used, but not limited thereto. And, it is preferable that B ³ of Formula 6 is silicon, but is not limited thereto.

The metallocene compound represented by Chemical Formula 6 in the metallocene compound mainly contributes to making a high molecular weight copolymer having a high SCB (short chain branch) content, and the metallocene compound represented by Formula 3 is mainly a low SCB. The content may contribute to making a low molecular weight copolymer. The metallocene compound represented by Formula 4 or 5 may also contribute to making a low molecular weight copolymer having a moderate SCB content.

In particular, the metallocene compound represented by Chemical Formula 6 forms an ligand structure in which an indeno indole derivative and a fluorene derivative are crosslinked by a bridge compound, and has a non-covalent electron pair capable of acting as a Lewis base to the ligand structure, thereby forming a Lewis of the carrier. It is supported on the surface having acidic properties and shows high polymerization activity even when supported. 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 hydrogen response is low and high activity is maintained even in the presence of hydrogen. Therefore, in the case of making a common supported catalyst system using such a transition metal compound, ultra-high molecular weight olefin polymers can be polymerized by stabilizing beta-hydrogen of the polymer chain in which nitrogen atoms of indenoindole derivatives are grown by hydrogen bonding. In addition, according to one embodiment of the present invention, by including at least two or more different metallocene compounds selected from the above formulas 3 to 6 is a high molecular weight olefin-based copolymer, and at the same time has a wide molecular weight distribution and excellent physical properties In addition, it is possible to manufacture polar olefins with excellent processability.

As a metallocene compound represented by the said Formula (3), for example

As the metallocene compound represented by Formula 4, for example

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

21

The common supported catalyst system is one in which at least one of the above-described metallocene compounds and at least one of the organic chromium compounds are supported on the carrier.

According to an embodiment of the present invention, the common supported catalyst system may further include one or more of an aluminum-containing agent of the formula (8), and a borate-based second catalyst of the formula (9).

[Formula 8]

-[AI (R ₂₆ ) -O] k- in Formula 8,

R ₂₆ are the same as or different from each other, and are each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a carbon atom substituted with halogen Hydrocarbyl radical of 20 to 20, k is an integer of 2 or more,

[Formula 9]

T ⁺ [BG ₄ ] ^"

In Formula 9,

T + is a polyvalent ion of +1, B is boron in +3 oxidation state, G is independently a hydride group, dialkyl amido group, halide group, alkoxide group, aryl oxide group, hydrocarbyl group, halo car It is selected from the group consisting of bil group and halo-substituted hydrocarbyl group, wherein G has up to 20 carbons, but at less than one position, G is a halide group.

By the use of such first and second cocatalysts, the polymerization activity can be improved while the molecular weight distribution of the finally produced polyolefin becomes more uniform.

The first cocatalyst of Chemical Formula 8 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular or reticular form, and specific examples of the first cocatalyst include methylaluminoxane (MAO) and ethylaluminoxane. , Isobutyl aluminoxane or butyl aluminoxane.

In addition, the second cocatalyst of Chemical Formula 9 may be a borate-based compound in the form of trisubstituted ammonium salt, dialkyl ammonium salt, or trisubstituted phosphonium salt. Specific examples of the second cocatalyst include trimetalammonium tetra Phenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, methyltetracyclocyclodecylammonium tetraphenylborate, N, Ν-dimethylaninium tetraphenylborate, Ν, Ν-diethylaninium tetraphenylborate, Ν, Ν-dimethyl (2,4,6-trimethylaninynium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl Borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluor Phenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate,

Tripropylammonium tetrakis (pentafluorophenyl) borate, tri (η-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary- Butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylaninium tetrakis (pentafluorophenyl) borate, Ν, Ν- diethylaninium tetrakis (pentafluorophenyl) borate, ^ 1 \ 1-dimethyl (2,4,6-trimethylaninium) 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 tetra Keith (2,3,4,6-, tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, Ν, Ν-dimethylaninynium Tetrakis (2,3,4,6-tetrafluorophenyl) borate, Ν, Ν-diethylaninynium Tetrakis (2,3,4,6-tetrafluorophenyl) borate or Ν, Ν-dimethyl- Borate compounds in the form of trisubstituted ammonium salts such as (2,4,6-trimethylaninynium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate; Borate type in the form of dialkylammonium salt, such as dioctadecyl ammonium tetrakis (pentafluorophenyl) borate, ditetradecyl ammonium tetrakis (pentafluorophenyl) borate, or dicyclonuclear ammonium tetrakis (pentafluorophenyl) borate compound; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl And borate compounds in the form of trisubstituted phosphonium salts such as borate.

In the catalyst composition of the present invention, in order to increase the selectivity to linear alpha-olefins and to increase oligomerization and copolymerization reaction activity, the molar ratio of the organic cream compound to the metallocene compound is about 10: 1 based on the transition metal. It may be about 1:10, preferably about 1: 5 to about 5: 1, but the present invention is not limited thereto, and the poly ratio to be produced may be controlled in various molar ratios according to lepin. In the common supported catalyst system, the mass ratio of the total transition metal to the carrier included in the metallocene compound and the organic chromium compound may be 1:10 to 1: 1,000. When including the carrier by the mass ratio, In addition, the mass ratio of the promoter compound carrier may be 1: 1 to 1: 100. In the method for producing the polyolefin, the carrier may be a carrier containing a hydroxy group on the surface, and preferably a carrier having a highly reactive hydroxyl group and a siloxane group which are dried to remove moisture on the surface. Can be used.

For example, silica, silica-alumina, and silica-magnesia dried at high temperatures may be used, which are typically oxides, carbonates, sulfates, and the like, such as Na ₂ O, K ₂ CO 3, BaSO ₄ , and Mg (NO ₃ ) ₂ . May contain nitrates.

The drying temperature of the carrier is preferably about 200 to 800 ^° C, more preferably about 300 to 600 ^° C, and most preferably about 300 to 400 ^° C. Moisture when the carrier has a drying temperature of less than about 200 ^° C If there is too much water on the surface, the cocatalyst reacts, and if it exceeds about 800 ° C, the pores on the surface of the carrier are combined to reduce the surface area, and also the surface of the hydroxy group disappears and only siloxane groups remain. It is not preferable because the reaction space is reduced. The amount of hydroxyl groups on the surface of the carrier is preferably about 0.1 to 10 mm / g, more preferably about 0.5 to 1 mm / g. The amount of the hydroxyl groups on the surface of the carrier is a method and conditions for preparing the carrier or drying conditions. For example, it can be adjusted by temperature, time, vacuum or spray drying.

If the amount of the hydroxy group is less than about 0.1 mmol / g, the reaction site with the promoter is small. If the amount of the hydroxy group is greater than about 10 mmol / g, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. Not desirable

In a catalyst system comprising the organic chromium compound, the metallocene compound, and the cocatalyst, the components of the catalyst system are active at the same time or in any order, added together in the presence or absence of monomers in any suitable solvent to make the catalyst active. Can be obtained. Suitable solvents include, but are not limited to, heptane, toluene, cyclonucleic acid, methylcyclonucleic acid, 1-nuxene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, and the like. Do not. The common supported catalyst system according to the present invention may be prepared by, for example, supporting a cocatalyst compound on a carrier, supporting a metallocene compound on the carrier, and supporting an organic chromium compound on the carrier. .

In the method for preparing the common supported catalyst, the order of the step of supporting the metallocene compound and the step of supporting the organic chromium compound may be changed as necessary. That is, the metallocene compound is first supported on the carrier. Thereafter, the supported organic catalyst compound may be further supported to produce a supported catalyst, or the organic chromium compound may be supported on a carrier first, and then the supported metallocene compound may be further supported to prepare a supported catalyst.

On the other hand, according to another embodiment of the present invention, there can be provided a method for producing a polyolefin, including the step of polymerizing an olefin monomer in the presence of the above-described common supported catalyst system.

Using the common supported catalyst system of the above embodiment, there is no need to perform a separate process for preparing alpha-olefins, or additionally add comonomers, and simultaneously perform oligomerization and copolymerization of olefin monomers in a single reactor with high efficiency. Can be.

Ethylene may be preferably used as the olefin monomer.

The preparation of the polyolefin according to the present invention can be carried out preferably using ethylene as the olefin monomer, using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

The common supported catalyst system is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, nucleic acid, heptane, nonane, decane, and isomers thereof, such as aromatic hydrocarbon solvents such as benzene, dichloromethane and chlorobenzene. It may be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom, and then injected into a reaction system. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further use of a promoter.

The step of polymerizing the lepin monomer may be carried out at a temperature of about 5 ^° C. to about 20 ^° C., preferably at a temperature of about 30 ° C. to about 150 ° C. In addition, the step of polymerizing the olefinic monomer is at a pressure of about 1 bar to about 300 bar, Preferably it can be carried out at a pressure of about 2 bar to about 150 bar.

According to one embodiment of the present invention, the polymerization can be carried out by supplying the lepin-based monomer in the presence of hydrogen gas.

At this time, the hydrogen gas serves to suppress the rapid reaction of the metallocene compound of the initial polymerization to produce a higher amount of high molecular weight polyolefin. Therefore, by using such a hydrogen gas, a higher molecular weight and Polyolefins with a broad molecular weight distribution can be obtained effectively.

The hydrogen gas may be introduced such that the molar ratio of hydrogen gas: an olefinic monomer is about 1: 100 to 1: 1,000. When the amount of the hydrogen gas is too small, the catalytic activity is not sufficiently realized, so that the desired molecular weight and molecular weight distribution can be obtained. The production of polyolefins may be difficult to obtain, and the addition of excessive amounts of hydrogen gas may not provide sufficient catalytic activity.

When the common supported catalyst system and the olefin monomers such as ethylene are reacted, each of the organic chromium compound and the metallocene compound supported on the common supported catalyst system and the olefinic monomers in contact with each other are multiplied (oligomerization). Reaction) and polymerization reaction of the olefinic monomer. At this time, in the method for washing polyolefins of the present invention, the oligomerization reaction and polymerization reaction are not limited to sequentially occurring, and each metallocene compound or organic cream compound supported on the common supported catalyst system and an olefin resin monomer are used. At the same time, they may occur sequentially or randomly, depending on their contact with.

On the other hand, alpha-olefins such as propylene, 1-butene, 1-octene, and 1-nuxene produced by the contact between the organic chromium compound and the olefinic monomer are present in or near the supported catalyst system. Therefore, the alpha-olefin produced by the organic cream compound supported on the common supported catalyst system is highly in contact with the metallocene compound, and is much higher than in the general olefin copolymerization reaction in which the alpha-olefin is introduced into the reaction system separately from the catalyst system. do. Therefore, the amount of alpha-olefins that cannot be introduced into the polyolefin is reduced, and the comonomer conversion is increased to increase the content of SCB (short chain branch) and LCB (long chain branch) in the polyolefin, thereby producing high quality linear low density polyethylene. In addition, there is no need to add expensive comonomers separately. This reduces the production cost of the final product.

Hereinafter, the present invention will be described in detail with reference to Examples. However, these embodiments may be modified in various forms, and the scope of the present invention should not be interpreted as being limited by the embodiments described below.

Compound Synthesis

All reactions were performed under argon using Schlenk technique or glove box. Synthesized compounds were analyzed by ¹ H (500 MHz) and ³¹ P (202 MHz) NMR spectra using a Varian 500 MHz spectrometer. The shift is expressed in ppm in the downfield from TMS with the residual solvent peak as reference. Phosphorous probes were calibrated with aqueous H ₃ PO ₄ Example of synthesis of organic cream compounds

Synthesis Example 1

1 synthetic

Under argon, 3- (aminomethyl) -3,5,5-trimethylcyclohexanamine (5 mmol) and triethylamine (3-10 equiv. To amine) were dissolved in dichloromethane (80 mL). While the flask was immersed in a water bath, chlorodiphenylphosphine (20 mmol, 2 equiv. To amine) was added slowly and stirred overnight. After blowing the solvent in vacuo, THF was added and sufficiently stirred to remove triethylammonium chloride salt with an air-free glass filter. The solvent was removed from the filtrate to obtain the product.

P NMR (202 MHz, CDCI ₃ ): 45.6 (br s), 56.2 (br s)

¹ -2> Synthesis of Organic Cream Compound 0.3 ml of chromium (IN) acetylacetonate (Cr (acac) ₃ ) under argon gas and 0.15 mm of the ligand compound prepared according to Synthesis Example 1-1 were placed in a flask. 100 ml_ of dichloromethane (CH ₂ CI ₂ ) was added thereto, followed by stirring for at least 1 hour, dried under reduced pressure to remove dichloromethane, and 65 ml_ of toluene was added thereto to prepare an organic cream compound solution. Synthesis Example 2

An organic cream compound solution was prepared in the same manner as in Synthesis Example 1, except that 0.124 mmol of acetylacetonate (Cr (acac) ₃ ) and 0.062 mmol of the ligand compound were used in Synthesis Example 1. Synthesis Example of Metallocene Compound

Synthesis Example 3: (tBu-O- (CH _? ) _Fi -CsH ₄ ) _? ZrCI _?

Using 6-chlorohexanol (6-chlorohexan) to prepare t-Butyl-0- (CH ₂ ) ₆ -CI by the method shown in Tetrahedron Lett. 2951 (1988), to which NaCp was reacted t-Butyl-0- (CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80 ^° CI 0.1 mmHg).

In addition, dissolve t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ in THF at -78 ^° C, and slowly add normal butyllithium (n-BuLi), and then warmed up to room temperature, reaction for 8 hours I was. The solution was then slowly stirred with a pre-synthesized lithium salt solution in a suspension solution of ZrCI ₄ (THF) ₂ (1.70 g, 4.50 mmol) / THF (30 mL) at -78 ^° C. The reaction was further performed at room temperature for 6 hours.

All volatiles were dried in vacuo, and the resulting oily liquid material was filtered off by adding hexane solvent. The filtered solution was vacuum dried and the nucleic acid was added to induce precipitate ^at low temperature (-20 ^° C). Filtering at low temperature gave a white solid [tBu-0- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCI ₂ compound (yield 92%).

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

3C NMR (CDCI ₃ ): 135.09, 1 16.66, 1 12.28, 72.42, 61 .52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00. Synthesis Example 4 (tBu-O- (CH _? ) G) (CH.) Si (Cg (CHg) ₄ ) (tBu-N) TiC

50 g of Mg (s) was added to a 10 L reactor at room temperature, followed by 300 ml of THF. After about 0.5 g was added, the reaction temperature was maintained at 50 ^° C. After the reactor temperature 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. It was observed that the reaction temperature increased by 4 to 5 ^° C. with the addition of 6-t-butoxynuclear chloride. The mixture was stirred for 12 hours while adding 6-t-butoxynuxyl chloride. After 12 hours of reaction, a black reaction solution was obtained. After taking 2 mL of the resulting black solution, water was added to obtain an organic layer, and 6-t-buthoxyhexane was identified by 1 H-NMR. Grignard from the 6-t-butoxynucleic acid. (Gringanrd) The reaction was well done. Thus, 6-t-buthoxyhexyl magnesium ch oride was synthesized.

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

It was angled up to 20 ^° C. 560 g of the synthesized 6-t-butoxynucleus magnesium chloride was added to the reaction vessel at a rate of 5 mL / min using a feeding pump. After the feeding of the Grignard reagent (feeding) was completed, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. It was confirmed that white MgCI ₂ salt was formed after 12 hours of reaction. 4 L of nucleic acid was added to remove the salt through a labdori to obtain a filter solution. After adding the obtained filter solution to the reactor, the nucleic acid was removed at 70 ^° C to obtain a pale yellow liquid. The obtained liquid was identified to be the desired methyl (6-t-buthoxy hexyl) dichlorosilane} compound through 1 H-NMRol.

1 H-NMR (CDCI ₃ ): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1

(m, 2H), 0.7 (s, 3H)

1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reaction vessel and the reaction temperature was -20 ^° C. It was added to the reactor at a rate of 5 mL / min using n-BuLi 480 ml_feeding pump. After adding n-BuU, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, an equivalent of methyl (6-t-butthoxy hexyl) dichlorosilane (326 g, 350 mL) was added quickly to the reactor. After stirring for 12 hours while slowly raising the reaction temperature to room temperature, the reactor temperature was again changed to 0 ^° C., and then 2 equivalents of t-BuNH ₂ was added thereto. 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 the filter solution was added to the reaction vessel again, the nucleic acid was removed at 70 ^° C. to obtain a yellow solution. Obtain the yellow solution through 1 H-NMR through methyl (6-t-butoxynucleosil) (tetramethyl CpH) t-butylaminosilane (Methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylam

It was confirmed that the compound.

n-BuLi and ligand dimethyl (tetramethyl CpH) t-butylaminesilane

TiCI ₃ (THF) ₃ (10 mm) was quickly added to the dilithium salt of -78 ^° C ligand synthesized in THF solution from (Dimethyl (tetramethylCpH) t-Butylaminosilane). The semi-aqueous solution was slowly stirred at -78 ^° C for room temperature for 12 hours. After stirring for 12 hours, an equivalent amount of PbCI ₂ (10 mmol) was added to the semi-aqueous solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, the blue vagina obtained a black solution. After removing THF from the resulting semi-aqueous solution, nucleic acid was added to filter the product. After removing the nucleic acid from the resulting filter solution, the desired ([methyl (6-t-buthoxyhexyl) silyl (n5-tetramethylCp) (t-Butylamido)] TiCI ₂ ) from 1 H-NMR was (tBu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ (CH ₃ ) ₄ ) (tBu-N) TiCI ₂ .

1 H-NMR (CDCI ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1. Preparation Example of 2 (s, 9H), 0.7 (s, 3H) Common Supported Catalysts

Preparation Example 1

100 ml of toluene was added to room temperature and a glass reaction machine, 10 g of dried silica was added thereto, and the reaction mixture was stirred while raising the reaction temperature to 40 ^° C. After dispersing the silica evenly, 91 ml_ of 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, the temperature was raised to 80 ^° C., and the mixture was stirred at 200 rpm for 12 hours. After this, the temperature was lowered to 40 ^° C., and the unreacted aluminum was washed with a sufficient amount of layer with luene. The compound was removed. Again 100 mL of toluene was added, and 0.1 mmol of the metallocene compound prepared in Synthesis Example 4 was added thereto, followed by stirring for 1 hour. Secondly, 0.1 mmol of the metallocene compound prepared in Synthesis Example 3 was added thereto, followed by further reaction for 1 hour. Finally, after adding the organic cream compound solution prepared in Synthesis Example 1, the reaction was further added for 2 hours.

After the reaction was completed, the stirring was stopped, the luene layer was separated and removed, and then, the reduced pressure was removed at 40 ^° C. to remove the luene, thereby preparing a carrier catalyst. Preparation Example 2

In Preparation Example 1, except that the organic cream compound solution prepared in Synthesis Example 2 was used, a common supported catalyst was prepared in the same manner as in Preparation Example 1. Comparative Production Example 1

In Preparation Example 1, a metallocene supported catalyst was prepared in the same manner as in Preparation Example 1, except that no organic chromium compound solution was used. Polyolefin Polymerization Example

Example 1

10 mg of the common supported catalyst prepared in Preparation Example 1 was quantified in a dry box, placed in a 50 mL glass bottle, sealed with a rubber septum, and prepared from a dry box to prepare a catalyst to be injected. The polymerization was performed at a temperature equipped with a mechanical stirrer. It was performed in a 600 mL metal alloy reactor, which was adjustable and used at high pressure.

400 mL of nucleic acid containing 1.0 mmol triethylaluminum and the prepared supported catalyst were introduced into the reactor without air contact, and the gas ethylene monomer was continuously heated at a pressure of 30 Kgf / cm ² at 80 ° C. The polymerization was carried out for 1 hour. The termination of the polymerization was completed by first stopping the stirring and then removing the ethylene by exhausting.

The polymer obtained therefrom was filtered to remove most of the polymerization solvent and then dried for 4 hours in an 80 ° C vacuum oven. Example 2

In Example 1, polyolefin polymerization was carried out in the same manner as in Example 1 except that the common supported catalyst of Preparation Example 2 was used. Example 3

The polymerization was carried out using the supported catalyst of Preparation Example 2 in Example 1

Polyolefin polymerization was carried out in the same manner as in Example 1 except that the reaction was carried out at 85 ^° C. Example 4

In Example 1, polyolefin polymerization was carried out in the same manner as in Example 1, except that the supported catalyst of Preparation Example 2 was used, and hydrogen was added at 0.03% relative to ethylene. Comparative Example 1

Except for using the common supported catalyst of Comparative Preparation Example 1 in Example 1 _. Polyolefin polymerization was carried out in the same manner as in Example 1. Comparative Example 2

In Example 1, polyolefin polymerization was carried out in the same manner as in Example 1, except that the support catalyst of Comparative Preparation Example 1 was used, and 13.5 g of 1-nuexene was added. The supported catalyst, polymerization conditions, polymerization activity, molecular weight and molecular weight distribution of the obtained polymers used in Examples and Comparative Examples are shown in Table 1 below. TABLE 1

In Table 1, the content of the alpha olefin in the polyolefin was confirmed by calculating the molar ratio of the branch chain of each sample after normalizing the integration value of the main chain to 1000 in the 1 H NMR spectrum. More specifically, when the analytical value having different structure ends is obtained from the co-polymerized polyolefin, the rest of the co-polymerized polyolefin is estimated except for the end of the structure having a double bond (that is, the alpha-olefin not used for the co-polymerization). The chain to 1000 Placed and calculated as the ratio of relative ends. At this time, it is assumed that structures having a double bond at the terminal are produced in the same molar ratio with the same molecular weight. Referring to Table 1, Comparative Example 1 was confirmed that there is no copolymer phosphorus by copolymerizing only ethylene without a comonomer using only a supported catalyst on which a metallocene compound is supported.

Comparative Example 2 was polymerized by using only a metallocene supported catalyst and adding 1-nuxene as a comonomer, and as a result, it was confirmed that 1-nuxene copolymerized polyolefin was produced. Although 13.5 g was added, it was confirmed that about 13.0 g of 1-nucleene remained in the filtrate after synthesis, and an equivalent amount of 1-nuxene remained in the copolymerization.

On the other hand, in Examples 1 to 4 using a supported catalyst supported by an organic chromium compound and a metallocene compound, and subjected to a copolymerization process using only ethylene, alpha olefins were higher than that of Comparative Example 2, even though no comonomer was used. As a result, it was confirmed that copolymerization was carried out at the molar ratio of the level. Thus, the ethylene was enzymatically enzymatically formed by the supported catalyst of the present invention to produce an alpha olefin comonomer such as 1-nucleene, and the comonomer thus produced was successfully copolymerized. It can be seen that it was introduced in. .

In addition, it was confirmed by the GC analysis that the presence of 1-nuxene and 1-octene in the synthetic filtrate in Examples 1 to 4, and confirmed that various comonomers such as 1-octene as well as 1-nuxene were produced. . In particular, in all the examples, the amount of alpha olefins introduced into the polyolefin was higher than that of Comparative Example 2, but the amount of alpha olepin remaining after polymerization was lower than that of Comparative Example 2, so that the concentration of low comonomer in the reaction system was reduced. It can be interpreted that the same level of comonomers were injected, and therefore, the catalyst system of the present invention showed a high incidence of comonomers.

Claims

Claims [Claim 1] The molecule contains at least two groups represented by the following formula (1), and at least one of the groups represented by the formula (1) has a coordination bond with a cr (Cr) to a factor (P). 그룹 a group (L) connecting each of the two or more groups with 4 to 8 carbon atoms, each having 2 to 20 carbon aliphatic groups, 2 to 20 heteroaliphatic groups, 2 to 20 carbon alicyclic groups, At least one organic cream compound having a heterocyclic group having 2 to 20 carbon atoms, or a group having two or more kinds of the aliphatic group, heteroaliphatic group, alicyclic group, and heteroalicyclic group; and metallocene compound One or more carriers supported on the carrier:

[Formula 1]

^R 、人

2 R3

In Chemical Formula 1,

Ri to ᅵ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl alkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, or 7 to 20 carbon atoms. It is a 20 alkoxy aryl group.

[Claim 2]

The catalyst supported catalyst system of claim 1, wherein the group (L) is a group selected from the group consisting of the above formulas:

In the above formulas,

^* Is a site that binds to N in Formula 1,

R 'is independently hydrogen or alkyl of 1 to 5 carbon atoms, p is an integer from 1 to 6, q is an integer from 1 to 5, and a plurality of R' bonded to one ring may be the same or different from each other. have.

[Claim 3]

According to claim 1, The organic chromium compound is represented by the following formula 1-1, Supported catalyst system:

[Formula 1-1]

In Chemical Formula 1 -1, L is a group connecting 4 to 8 carbon atoms between nitrogen (N) atoms, an aliphatic group having 2 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, an alicyclic group having 2 to 20 carbon atoms, and having 2 to 20 carbon atoms. A heteroalicyclic group of 20, or a group in which two or more kinds of the aliphatic group, heteroaliphatic group, alicyclic group, and heteroalicyclic group are bonded;

Ri to R ₄ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a arylalkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, or 7 to 20 carbon atoms. 20 alkoxyaryl groups;

Y ^ to Y ₃ are each independently halogen, hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or a heterohydrocarbyl group having 1 to 10 carbon atoms.

[Claim 4]

According to claim 1, The organic chromium compound is represented by the formula 1-2, a common supported catalyst system:

[

In the above formula 1 -2,

L is a group connecting 4 to 8 carbon atoms between nitrogen (N) atoms, an aliphatic group having 2 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, an alicyclic group having 2 to 20 carbon atoms, and having 2 to 20 carbon atoms A heteroalicyclic group of 20, or the aliphatic group ᅳ heteroaliphatic group, alicyclic group, and heteroalicyclic group is a group of two or more bonded,

To F are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or 7 to 20 carbon atoms 20 alkoxyaryl group; Y ₁ to X ₃ are each independently halogen, hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or a heterohydrocarbyl group having 1 to 10 carbon atoms. [Claim 5]

The common supported catalyst system according to claim 1, wherein Ri to R ₄ in Formula 1 are phenyl. [Claim 6]

The method of claim 1, wherein the metallocene compound comprises at least one selected from compounds represented by the following Chemical Formulas 3 to 6, Supported catalyst system:

[Formula 3]

(Cp ¹ R ^a ) _n (Cp ² R ^b ) MZ ¹ _3-n

In Formula 3,

M ¹ is a Group 4 transition metal;

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

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

m is 1 or 0;

[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 cyclopentadienyl, indenyl, 4, 5,

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

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 to C10 alkynyl; Z ³ silver 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;

[

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 A C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

D is -0-, -S-, -N (R)-or -Si (R) (R ')-, where R and R' are the same as or different from each other, and are 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;

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

B ³ 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, C 1 to C 20 alkyl group, C 2 to C 20 alkenyl group, C 6 to C 20 aryl group, nitro group, amido group, C 1 to C 20 alkylsilyl group Or 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 Chemical Formulas 7a, 7b, or 7c, except that C ¹ and C ^{2 are} both of Chemical Formula 7c;

In Formulas 7a, 7b, and 7c,

R9 to R25 and R9 'to R17' 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 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 adjacent to R18 to R25 The foregoing can be linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

[Claim 7]

The method of claim 1, further comprising at least one of the aluminum-containing first cocatalyst of the formula (8), and the borate-based second cocatalyst of the general formula (9):

[Formula 8]

-[AI (R ₂₆ ) -0] _k -in Formula 8,

R ₂₆ are the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, k is an integer of 2 or more,

[Formula 9]

T ⁺ [BG ₄ ] ^"

In Formula 9,

T ⁺ is a + monovalent polyvalent ion, B is a boron in +3 oxidation state, G is independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryl oxide group, a hydrocarbyl group, a halo Selected from the group consisting of a carbyl group and a halo-substituted hydrocarbyl group, wherein G has up to 20 carbons, but at less than one position G is a halide group. [Claim 8]

The support catalyst system of claim 1 wherein the carrier is selected from the group consisting of silica, silica-alumina and silica-magnesia.

[Claim 9]

A process for producing a polyolefin, comprising polymerizing an olefinic monomer in the presence of the common supported catalyst system of claim 1.

[Claim 10]

10. The method of claim 9, wherein the olefinic monomer is ethylene.

[Claim 1 11]

10. The method of claim 9, wherein the step of polymerizing the lepin monomers,

Obtaining ethylene oligomer by reacting the olefinic monomer with oligomerization; and

And polymerizing the ethylene oligomer produced by the multimerization reaction with the olefinic monomer (p ymerization) to obtain a polyolefin.

[Claim 12]

The method of claim 1, further comprising: obtaining the ethylene oligomer; And the step of obtaining the polyolefin is carried out continuously or simultaneously in the same reactor.

[Claim 13]

The method of claim 9, wherein the polymerizing the olefinic monomer is performed at a temperature of 5 to 200 ^° C. 11.

[Claim 14]

The method of claim 9, wherein the polymerizing the olefinic monomer is performed at a pressure of 1 to 300 bar.