KR20120090479A - New transition metal compound, new organic ligand compound, catalysts composition comprising the transition metal compound and preparation method of poly-olefin using the catalysts composition - Google Patents

Abstract

PURPOSE: A method for polyolefin using transition metal catalyst compositions and catalyst compositions is provided to ensure high reactivity in poly olefin polymerization and to easily control workability and mechanical property of polyolefin. CONSTITUTION: A transition metal compound is denoted by chemical formula 1, 2, or 3. An organic ligand compound is denoted by chemical formula 5, 6, or 7. A transition metal catalyst composition contains the transition metal compound and co-catalyst. The co-catalyst contains a compound of chemical formula 11([L-H]+[Z(E)4]- or [L]+[Z(E)4]-), 12(D(R9)3), or 13. A method for preparing polyolefin comprises a step of polymerizing olefin monomers under the presence of the transition metal catalyst composition. The olefin monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-hepten, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, or norbornene.

Description

A novel transition metal compound, a novel organic ligand compound, a transition metal catalyst composition comprising the transition metal compound, and a method for producing a polyolefin using the catalyst composition TECHNICAL FIELD METAL COMPOUND AND PREPARATION METHOD OF POLY-OLEFIN USING THE CATALYSTS COMPOSITION}

The present invention relates to a novel transition metal compound, a novel organic ligand compound, a metallocene catalyst composition comprising the transition metal compound, and a method for producing a polyolefin using the catalyst composition, and more particularly, a polyolefin polymerization reaction. A novel transition metal compound, a novel organic ligand compound, and a novel transition metal compound that can exhibit high reactivity and can easily control properties such as chemical structure, molecular weight distribution, and mechanical properties of the synthesized polyolefin. It relates to a transition metal catalyst composition comprising and a method for producing a polyolefin using the catalyst composition.

Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used in the commercial production process of conventional polyolefins. The Ziegler-Natta catalysts have high activity, but because they are multi-site catalysts, the molecular weight distribution of the resulting polymers is wide and Since the composition distribution of the monomer was not uniform, there was a limit to securing desired physical properties.

Accordingly, recently, metallocene catalysts in which a ligand including a cyclopentadiene functional group and a transition metal such as titanium, zirconium, and hafnium have been developed have been widely used. These metallocene catalysts are single active site catalysts with one type of active site, and have a narrow molecular weight distribution of the produced polymer and can greatly control the molecular weight, stereoregularity, crystallinity, and especially the reactivity of the comonomer, depending on the structure of the catalyst and the ligand. There is an advantage. However, the polyolefin polymerized with a metallocene catalyst has a narrow molecular weight distribution, and thus, when applied to some products, various attempts have been made to solve the problem because it is difficult to apply the field such as productivity is significantly decreased due to the extruded load.

[Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (Constrained-Geometry Catalyst, CGC), developed by DOW in the early 1990s, compared to the known metalocene catalyst in the copolymerization reaction of ethylene and alpha-olefin (1 ) It has high activity even at high polymerization temperature and produces high molecular weight polymer. (2) It is excellent in that it can easily synthesize alpha-olefin with high steric hindrance such as 1-hexene and 1-octene.

As various properties of CGC are gradually known, various attempts have been actively made to synthesize derivatives thereof and use them as polymerization catalysts. For example, instead of a silicon bridge, various other bridges and nitrogen compounds have been introduced, and the synthesis of polyolefins has been attempted using them. Representative metal compounds known to date are listed below.

1

2

3

4

One

2

3

4

The compounds listed above have phosphorus (1), ethylene or propylene (2), methylidene (3), and methylene (4) bridges instead of the CGC-structured silicon bridges, respectively. The copolymerization of did not give excellent results in terms of activity or copolymerization performance compared to CGC.

In addition, many compounds composed of an oxido ligand instead of the amido ligand of CGC have been synthesized, and the synthesis of polyolefins using the same has been partly attempted. The examples are as follows.

5

6

7

8

5

6

7

8

In addition, Sumitomo Co., Ltd. has introduced the synthesis of a catalyst 8 having a structure similar to the above compound and a high temperature and high pressure polymerization method using the same.

9

9

On the other hand, Mitsui, Japan, developed Group 4 transition metal compounds (Ti, Zr) based on phenoxy imine to synthesize polyethylene and polypropylene having various properties. A characteristic of the catalyst is that it does not include structurally the cyclopentadiene ligand, which is an important backbone of the existing metallocene catalyst or CGC. Accordingly, these catalysts have been in the spotlight as post-metallocenes, that is, next-generation catalysts that deviate from the metallocene structure. Since this catalyst was named as FI catalyst (10), as various substituents were changed around the catalyst backbone, the activity and efficiency of the catalyst were examined in detail and various studies were conducted.

10

10

Recently, LG Chem has introduced another bridge in the CGC backbone, i.e., a catalyst (11,12) having a ligand introduced with a phenyl group (Organometallics, 2006, 25, 5122 and 2008, 27, 3907). These catalysts are characterized by exhibiting at least the same level of activity, content of 1-octene and molecular weight distribution compared to conventional CGC in synthesizing ethylene / 1-octene copolymer.

11

12

11

12

However, the post metallocene catalyst which can be applied to a commercial process is not known much. Accordingly, it is possible to implement a higher polymerization performance and provide a post metallocene which can provide a polyolefin having excellent physical properties. There is still a need for research on catalysts.

The present invention is to provide a novel transition metal compound.

In addition, the present invention is to provide a novel organic ligand compound.

The present invention is to provide a transition metal catalyst composition that can not only exhibit high reactivity in the polyolefin polymerization reaction, but also can easily control properties such as chemical structure, molecular weight distribution, mechanical properties, etc. of the polyolefin to be synthesized.

In addition, the present invention is to provide a method for producing a polyolefin using the catalyst composition.

The present invention provides novel transition metal compounds having specific chemical structures.

The present invention also provides novel organic ligand compounds having specific chemical structures.

The present invention also provides a metallocene catalyst composition comprising the transition metal compound.

In addition, the present invention is to provide a method for producing a polyolefin using the catalyst composition.

Hereinafter, a novel transition metal compound, an organic ligand compound, a metallocene catalyst composition and a method for preparing polyolefin according to specific embodiments of the present invention will be described in more detail.

According to one embodiment of the invention, a transition metal compound of Formula 1 may be provided.

[Formula 1]

In Formula 1, R ₁ is a cycloalkyl of 1 to 20 carbon atoms substituted or unsubstituted with a halogen group, a cycloalkyl of 5 to 60 carbon atoms substituted or unsubstituted with a halogen group, of 6 to 60 carbon atoms unsubstituted or substituted with a halogen group Aryl, cycloalkenyl of 5 to 60 carbon atoms substituted or unsubstituted with a halogen group, alkenyl group of 2 to 20 carbon atoms substituted or unsubstituted with a halogen group, alkylaryl or halogen group of 7 to 60 carbon atoms substituted or unsubstituted with a halogen group Substituted or unsubstituted arylalkyl having 7 to 60 carbon atoms.

Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ and Q ₆ may be the same or different from each other, and each independently hydrogen, deuterium, halogen, nitrile, acetylene, amine, amide, carbon number 1 Alkoxy carbonyl groups of 20 to 20, alkanoyl groups of 1 to 20 carbon atoms, silyl groups, alkyl groups of 1 to 20 carbon atoms, alkenyl groups of 2 to 20 carbon atoms, aryl groups of 6 to 20 carbon atoms, and 4 carbon atoms It may be a heterocyclic group of 20 to 20, an alkoxy group of 1 to 20 carbon atoms or an aryloxy group of 6 to 20 carbon atoms, two or more of Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ and Q ₆ It may be linked to each other to form an aliphatic ring or an aromatic ring.

In addition, Cy1 and Cy2 may be the same as or different from each other, and each independently include a nitrogen atom, and hydrogen; halogen; An alkyl group having 1 to 20 carbon atoms; And an aliphatic ring having 4 to 10 carbon atoms unsubstituted or substituted with one or more functional groups selected from the group consisting of aryl groups having 6 to 20 carbon atoms. May form a ring.

In addition, M is a transition metal of Groups 3 to 12, preferably titanium (Ti), zirconium (Zr) or hafnium (Hf). And, Y ₁ is oxygen (O), nitrogen (N), sulfur (S) or phosphorus (P).

M and Y ₁ may be coordinatively bonded, and '→' means coordinating.

X ₁ and X ₂ may be the same as or different from each other, and each independently a halogen, 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 an alkylaryl group having 7 to 20 carbon atoms. , An arylalkyl group having 7 to 20 carbon atoms, an alkyl amido group having 1 to 20 carbon atoms, an aryl amido group having 6 to 20 carbon atoms, or an alkylidene having 1 to 20 carbon atoms.

The present inventors have newly synthesized a transition metal compound containing a previously unknown organic ligand, and by appropriately adjusting the substituents introduced into the organic ligand compound, the electronic and three-dimensional environment around the transition metal can be easily controlled. Experiments confirmed that the present invention can provide a transition metal catalyst which can not only exhibit high reactivity in the polyolefin polymerization but also easily control the chemical structure, molecular weight distribution, and mechanical properties of the polyolefin to be synthesized. Was completed.

In particular, the transition metal compound of Formula 1 has relatively high bonds between atoms and intermolecular bonds, and thus has a high temperature activity compared to the previous metallocene catalyst or a post metallocene catalyst (a catalyst without a cyclopentadienyl ligand). Can have

When described in detail for each substituent in the above formula.

The alkyl group having 1 to 20 carbon atoms may include a linear or branched alkyl group, and the alkenyl group having 2 to 20 carbon atoms may include a straight or branched alkenyl group.

The silyl group may include a silyl functional group having an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 20 carbon atoms, or the like. , Specific examples of this Trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris (trimethylsilyl) silyl, and the like. It is not limited only to.

The aryl group is preferably an aromatic ring having 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.

The alkylaryl group refers to an aryl group having one or more linear or branched alkyl groups of 1 to 20 carbon atoms introduced therein, and the arylalkyl group refers to a straight or branched alkyl group having one or more aryl groups of 6 to 20 carbon atoms introduced thereto.

The alkyl amido group refers to an amido group in which a linear or branched alkyl group having 1 to 20 carbon atoms has 1 or more introduced thereto, and specifically, a dimethyl amido group, a diethylamido group, and the like, but is not limited thereto.

The aryl amido group means an amido group into which one or more aryl groups having 6 to 20 carbon atoms are introduced, and specifically, a diphenylamido group, but is not limited thereto.

The aryl oxy group means an aryl functional group to which an oxygen atom is introduced, that is, a functional group represented by '-O-Ar'.

The halogen group means fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and asatin (At).

The nitrile group may be represented by '-C≡N', and the acetylene group may be represented by '-C≡CH'.

In addition, the amide group may be represented as '-C (= O) -NH ₂ '.

On the other hand, preferred examples of the transition metal compound of Formula 1 include a compound of Formula 2 below.

(2)

In Formula 2, the contents of R ₁ , Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q _{6 ,} M, Y ₁ , X ₁ and X ₂ are the same as in Formula 1.

In Formula 2, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be the same or different from each other, each independently hydrogen, an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, It may be an allyl group having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

And, more preferable examples of the formula (1) include a compound of formula (3).

[Formula 3]

In Formula 3, R1 may be a phenyl group, a cyclohexyl group, methyl, ethyl, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group or tert-butyl group, X ₁ and X ₂ May be the same as or different from each other, and each independently may be halogen, phenyl group, cyclohexyl group, methyl, ethyl, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group or tert-butyl group .

Specific examples of Chemical Formula 3 may include a compound of Chemical Formulas 31 to 36, but are not limited thereto.

Formula 31

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

Meanwhile, according to another embodiment of the present invention, an organic ligand compound of Formula 5 may be provided.

[Formula 5]

In Formula 5, the contents of R ₁ , Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q _{6 ,} Y ₁ , Cy ₁ , and Cy ₂ are the same as described above in Formula 1.

As described above, the inventors have synthesized a previously unknown ligand, and by appropriately adjusting the substituents introduced into the organic ligand compound of Formula 4, the inventors can easily control the electronic and three-dimensional environment of the transition metal when the transition metal compound is formed. The experiment confirmed that it can be completed the invention . Accordingly, by using the organic ligand compound, a transition metal catalyst which can not only exhibit high reactivity in the polyolefin polymerization reaction but also easily control the properties such as chemical structure, molecular weight distribution, and mechanical properties of the polyolefin to be synthesized. Can provide.

After adding alkyl lithium to the organic ligand compound of Formula 5, and then adding a salt of a transition metal, it is possible to obtain a transition metal compound of Formula 1, 2 or 3.

On the other hand, as a preferred example of the organic ligand compound of Formula 5 may be a compound of the formula (6).

[Formula 6]

In Chemical Formula 6, R ₁ , Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q ₆ and The content of Y ₁ is as described above in Chemical Formula 1, and the content of R ₂ , R ₃ , R ₄ , R ₅ , R _6, and R ₇ is as described in Chemical Formula 2. And, more specific information regarding the formula (5) or (6) is as described above with respect to formula (1) or (2).

On the other hand, as a more preferred example of the organic ligand compound of Formula 5 may be a compound of the formula (7).

[Formula 7]

In Formula 7, R 1 may be a phenyl group, a cyclohexyl group, methyl, ethyl, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group or tert-butyl group.

Specific examples of Chemical Formula 7 include, but are not limited to, the compounds represented by Chemical Formulas 71 to 76 below.

[Formula 71]

[Formula 72]

[73]

[Formula 74]

[Formula 75]

[Formula 76]

The organic ligand compound of Formula 5 is a step of reacting the compound of Formula 51 with alkyl lithium, and then reacts with carbon dioxide and alkyl lithium; And it can be obtained through the step of reacting the result of the step with the formula (52).

[Formula 51]

또는

or

In Formula 51, the contents of Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q _{6 ,} Cy _{1 , and} Cy 2 are the same as described above in Chemical Formula 1.

[Formula 52]

In Formula 52, the contents of R ₁ and Y ₁ are the same as described above in Formula 1. In addition, X ₁₁ and X ₁₂ may be the same as or different from each other, and each may be halogen, preferably chlorine (Cl) or bromine (Br).

Meanwhile, the transition metal compound of Formula 1 may be obtained by reacting the compound of Formula 53 with the organic ligand compound of Formula 5.

[Formula 53]

In Formula 53, the contents of M, X ₁ and X ₂ are the same as those described in Formula 1 above. X ₁₃ may be the same as or different from X ₁ and X _2, and a halogen, 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 an alkyl having 7 to 20 carbon atoms. It may be an aryl group, an arylalkyl group having 7 to 20 carbon atoms, an alkyl amido group having 1 to 20 carbon atoms, an aryl amido group having 6 to 20 carbon atoms, or an alkylidene having 1 to 20 carbon atoms.

Specific examples of the preparation method of the transition metal compound of Formula 1 and the organic ligand compound of Formula 5 are shown in Scheme 1 below. However, the preparation method is not limited to the following Scheme 1.

[Scheme 1]

Meanwhile, according to another embodiment of the present invention, a transition metal catalyst composition including the transition metal compound of Formula 1 may be provided.

As described above, the transition metal compound of Chemical Formula 1 may be introduced into a novel organic ligand compound to easily control the electronic and three-dimensional environment of the transition metal, so that the chemical structure of the polyolefin synthesized using such a transition metal compound A catalyst composition capable of easily adjusting properties such as molecular weight distribution and mechanical properties may be provided.

On the other hand, the transition metal catalyst composition may further comprise a promoter. Specific examples of such cocatalysts include compounds represented by the following formulas 11 to 13 and mixtures of two or more thereof.

[Formula 11]

^{[LH] + [Z (E} ) 4] - or ^{[L] + [Z (E} ) 4] -

In Formula 11, L is a neutral or cationic Lewis acid, [LH] + or [L] ⁺ is a Bronsted acid, H is a hydrogen atom, Z is a Group 13 element (preferably +3 type oxidation) Boron or aluminum), and E may be the same or different from each other, and each independently one or more hydrogen atoms have 6 to 6 carbon atoms unsubstituted or substituted with a halogen, a hydrocarbyl having 1 to 20 carbon atoms, an alkoxy functional group or a phenoxy functional group. It is an aryl group of 20 or a C1-C20 alkyl group. The 'hydrocarbyl' is a monovalent functional group in which hydrogen atoms are removed from hydrocarbons, and may include ethyl, phenyl, and the like.

[Chemical Formula 12]

D (R ₉ ) ₃

In Formula 12, D is aluminum or boron, R ₉ may be the same or different from each other, and each independently halogen; Hydrocarbon groups having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen.

[Chemical Formula 13]

In Formula 13, R ₁₀ may be the same as or different from each other, and each independently a halogen group; Hydrocarbon groups having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen, a is an integer of 2 or more.

The compound of Formula 11 may play a role of activating the transition metal compound of Formula 1, and may include a non-coordinated anion compatible with cations which are Bronsted acids. Preferred anions are those that are relatively large in size and contain a single coordinating complex comprising a metalloid. In particular, compounds containing a single boron atom in the anion moiety are widely used. In view of this, salts containing anions containing coordinating complexes containing a single boron atom are preferred.

In the transition metal catalyst composition, the number of moles of the transition metal compound of Formula 1: The number of moles of the compound of Formula 11 may be 1: 1 to 1:10, preferably 1:10 to 1: 4. If the molar ratio is less than 1: 1, the amount of the promoter is relatively small, so that the activation of the metal compound may not be completed, and thus the activity of the transition metal catalyst may not be sufficient. Activity may increase, but the use of more promoters than necessary may cause a significant increase in production costs.

Specific examples of the compound of Formula 11 include triethylammonium tetra (phenyl) boron, tributylammonium tetra (phenyl) boron, trimethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethyl Ammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl ) Boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethylamidiumdium tetra (phenyl) boron, N, N-diethylanilidedium tetra (phenyl) boron, N, N- Diethylanilinium tetra (pentafluorophenyl) boron, diethyl ammonium tetra (pentafluorophenyl) boron, triphenyl phosphonium tetra (phenyl) boron, trimethyl phosphonium tetra (phenyl) boron, triethyl ammonium Tetra (phenyl) aluminum, tributylammon Niumtetra (phenyl) aluminum, trimethylammoniumtetra (phenyl) aluminum, tripropylammoniumtetra (phenyl) aluminum, trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (p-tolyl) aluminum, tri Ethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetra (penta) Fluorophenyl) aluminum, N, N-diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (pentafluoro Phenyl) aluminum, diethyl ammonium tetra (pentafluorophenyl) aluminum, triphenyl phosphonium tetra (phenyl) aluminum, trimethyl phosphonium tetra (phenyl) aluminum, triethyl ammonium tetra (phenyl) aluminum, Tributylammonium tetra (phenyl) aluminum, trimethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, tripropylammonium tetra (p-tolyl) Boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl ) Boron, N, N-diethylanilinium tetra (pentafluorophenyl) boron, diethyl ammonium tetra (pentafluorophenyl) boron, triphenyl phosphonium tetra (phenyl) boron, triphenyl carbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (pen) Tafluorophenyl) boron, trityltetra (pentafluorophenyl) boron, and the like, but are not limited thereto.

On the other hand, the compound of Formula 12 or 13 may serve as a scavenger to remove impurities that act as a poison to the catalyst in the reactant.

In the transition metal catalyst composition, the number of moles of the transition metal compound of Formula 1: The number of moles of the compound of Formula 12 or 13 is 1: 1 to 1: 5,000, preferably 1:10 to 1: 1,000, more preferably May be 1:20 to 1: 500. If the molar ratio is less than 1: 1, the effect of the addition of scavenger is insignificant, and if the molar ratio exceeds 1: 5,000, the excess alkyl group, which does not participate in the reaction, rather inhibits the catalytic reaction to act as a catalyst poison. As a result, a side reaction may occur to cause a problem of excess aluminum or boron remaining in the polymer.

Specific examples of the compound of Formula 12 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and trimethyl aluminum, triethyl aluminum or triisobutyl aluminum can be preferably used.

Specific examples of the compound of Formula 13 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like, and preferably methyl aluminoxane.

The catalyst composition may be a hydrocarbon solvent such as pentane, hexane, heptane, or the like; Or it may include an aromatic solvent such as benzene, toluene, but is not necessarily limited to this, a solvent known to be available for the transition metal catalyst may be used without particular limitation.

The transition metal compound and the promoter may be used in a state of being fixed to a carrier such as silica or alumina, but are not limited thereto.

The transition metal catalyst composition may be prepared by reacting the transition metal compound of Formula 1 with at least one promoter selected from the group consisting of the compounds of Formulas 11 to 13. For example, the transition metal compound of Formula 1 may be reacted with a promoter of the compound of Formula 12 or 13, and the reactant and the promoter of the compound of Formula 11 may be reacted to form a transition metal catalyst composition.

On the other hand, according to another embodiment of the invention, in the presence of the transition metal catalyst composition, there may be provided a method for producing a polyolefin comprising the step of polymerizing the olefin monomer.

As described above, the transition metal compound of Formula 1 can easily control the electronic and three-dimensional environment around the metal, can increase the yield of the polymerization reaction, the chemical structure, molecular weight distribution, mechanical properties, etc. of the polyolefin to be synthesized The characteristics of can be easily adjusted. In addition, the transition metal compound of Formula 1 has relatively high bonds between atoms and intermolecular bonds, and thus has a high temperature activity compared to a previous metallocene catalyst or a post metallocene catalyst (a catalyst without a cyclopentadienyl ligand). It can have a, it is possible to proceed with a high efficiency of the polymerization of the poly olefin in a high temperature range compared to the previous catalysts.

The polymerization reaction of the olefin monomer may be at least 90 ℃, preferably at 120 to 160 ℃. If the polymerization temperature is too low, the reactivity of the olefin monomer is not high, it may be difficult to synthesize the polyolefin, and if the polymerization temperature is too high, the olefin monomer may be thermally decomposed.

The polymerization reaction of the olefin monomer may be carried out in a continuous dissolution polymerization process, a bulk polymerization process, a suspension polymerization process or an emulsion polymerization process, but preferably by a solution polymerization reaction in a single reactor.

The reactor used in the production method is not particularly limited, but it is preferable to use a continuous stirred reactor (CSTR) or a continuous flow reactor (PFR). In the above production method, it is preferable that two or more reactors are arranged in series or in parallel, and further include a separator for continuously separating the solvent and the unreacted monomer from the reaction mixture.

When the production method of the polyolefin is carried out in a continuous solution polymerization process, it may be composed of a catalytic process, a polymerization process, a solvent separation process and a recovery process step, more specific details are as follows.

a) catalytic process

The transition metal catalyst composition may be injected by dissolving or diluting an aliphatic or aromatic solvent or the like. Aliphatic hydrocarbon solvents such as, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof; Aromatic hydrocarbon solvents such as toluene, xylene, benzene; Alternatively, the transition metal catalyst composition may be dissolved or diluted using a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene. Such a solvent can be treated with a small amount of alkylaluminum or the like to remove a small amount of water or air, which acts as a catalyst poison, and it is also possible to use an excessive amount of a promoter.

b) polymerization process

The polymerization process may be performed by reacting the transition metal catalyst composition and the olefin monomer in a reactor. In the polymerization process, when each reactant participates in the polymerization reaction in a solution phase and a slurry phase, a solvent may be injected into the reactor.

The molar ratio of the olefin monomer and the solvent in the polymerization reaction should be a ratio suitable for dissolving the raw material before the reaction and the polymer produced after the reaction. Specifically, the molar ratio of olefin monomer: solvent may be 10: 1 to 1: 10,000, preferably 5: 1 to 1: 100, most preferably 1: 1 to 1:20. When the molar ratio of the solvent is less than 10: 1, the amount of the solvent is too small to increase the viscosity of the fluid, which causes a problem in the transfer of the polymer, and when the molar ratio of the solvent exceeds 1: 10,000, Since the amount is more than necessary, problems such as an increase in equipment and an increase in energy costs due to the recirculation of the purification of the solvent may occur.

The solvent is preferably introduced into the reactor at a temperature of -40 ℃ to 150 ℃ using a heater or a freezer. When the temperature of the solvent is less than -40 ℃, there will be some differences depending on the reaction amount, but the temperature of the solvent is too low, the reaction temperature is also accompanied by the temperature control difficult problem, if the temperature exceeds 150 ℃ The temperature of the solvent is too high to control the reaction heat according to the reaction is difficult.

On the other hand, additional pumping between the reactor arrangement, pressure drop device and separator is achieved by supplying reactants (eg, solvents, olefin monomers, catalyst compositions, etc.) by raising the pressure above 50 bar using a high capacity pump. ) May be passed through a mixture of said feeds.

In the method for producing the polyolefin, the internal temperature of the reactor, that is, the polymerization reaction temperature may be -15 ℃ to 300 ℃, preferably 50 ℃ to 200 ℃, most preferably 100 ℃ to 200 ℃. If the internal temperature is less than -15 ℃, there is a problem that the reaction rate is low, the productivity is lowered, and if it exceeds 300 ℃ may cause problems such as the generation of impurities due to side reactions and discoloration, such as carbonization of the polymer.

In addition, in the method for producing the polyolefin, the internal pressure of the reactor may be 1 bar to 300 bar, preferably 30 to 200 bar, most preferably about 50 to 100 bar. When the internal pressure is less than 1 bar, the reaction rate is low, productivity is low, and there is a problem due to evaporation of the solvent used.

The polymer produced in the reactor is maintained at a concentration of less than 20 wt% in the solvent and is preferably passed to the first solvent separation process for solvent removal after a short residence time. The residence time of the resulting polymer in the reactor is 1 minute to 10 hours, preferably 3 minutes to 1 hour, most preferably 5 minutes to 30 minutes. If the residence time is less than 3 minutes, there is a problem such as productivity loss and catalyst loss due to a short residence time, and the increase in the manufacturing cost, etc., if more than 1 hour, depending on the reaction over the appropriate active period of the catalyst, The reactor is large and there is a problem of an increase in equipment costs.

c) solvent separation process

The solvent separation process is performed by varying the solution temperature and pressure to remove the solvent present with the polymer exiting the reactor. For example, the polymer solution transferred from the reactor is heated up from about 200 ° C. to 230 ° C. through a heater, and then the pressure is lowered through a pressure drop device to vaporize unreacted raw materials and solvent in the first separator.

At this time, the pressure in the separator may be 1 to 30 bar, preferably 1 to 10 bar, most preferably 3 to 8 bar, the temperature in the separator is 150 ℃ to 250 ℃, preferably 170 ℃ to 230 ℃, Most preferably, it may be 180 ℃ to 230 ℃.

If the pressure in the separator is less than 1bar, the content of the polymer is increased, there is a problem in the transfer, if it exceeds 30bar it may be difficult to separate the solvent used in the polymerization process. In addition, when the temperature in the separator is less than 150 ° C., the viscosity of the copolymer and its mixture is increased, and there is a problem in transporting. When the temperature is less than 250 ° C., color change may occur due to carbonization of the polymer due to high temperature.

The solvent vaporized in the separator can be recycled to the condensed reactor in the overhead system. The first step of solvent separation yields a polymer solution concentrated up to 65%, which is transferred to the second separator by a transfer pump through a heater, where the separation of residual solvent occurs. In order to prevent the deformation of the polymer due to high temperature while passing through the heater, a thermal stabilizer is added and a reaction inhibitor is injected into the heater together with the thermal stabilizer to suppress the reaction of the polymer due to the residual activity of the activator present in the polymer solution. do. The residual solvent in the polymer solution injected into the second separator is finally completely removed by a vacuum pump, and the granulated polymer can be obtained by passing through the cooling water and the cutting machine. The solvent and other unreacted monomers vaporized in the second separation process can be sent to a recovery process for purification and reuse.

d) Recovery process

The organic solvent added with the raw material to the polymerization process may be recycled to the polymerization process together with the unreacted raw material in the primary solvent separation process. However, the solvent recovered in the secondary solvent separation process contains a large amount of water that acts as a catalyst poison in the solvent due to contamination due to incorporation of a reaction inhibitor to stop the catalytic activity and steam supply from a vacuum pump, and thus after purification in a recovery process. It is preferred to be reused.

In the method for preparing the polyolefin, except for the above description, an apparatus, a device, a synthesis method, reaction conditions, and the like, which are known to be used for synthesizing the polyolefin using a metallocene catalyst, may be used without particular limitation.

Specific examples of the olefin monomer used in the method for producing the polyolefin include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene , 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aitosen, norbornene, norbornadiene, ethylidene nobodene, phenyl nobodene, vinyl nobodene, dicyclopentadiene , 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, or mixtures thereof.

According to the present invention, a novel transition metal compound which can exhibit high reactivity in a polyolefin polymerization reaction and can easily control the properties such as chemical structure, molecular weight distribution, processability, mechanical properties, etc. of the polyolefin to be synthesized, new An organic ligand compound, a transition metal catalyst composition, and a method for producing a polyolefin using the catalyst composition may be provided.

< Example  : Synthesis of Transition Metal Compounds>

Organic reagents and solvents were purchased from Aldrich and Merck and purified using standard methods. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment. Spectra were obtained using a 400 MHz nuclear magnetic resonator (NMR) to demonstrate the structure of the compound.

In the following examples, the term 'overnight' means approximately 12 to 16 hours, and 'room temperature' refers to a temperature of 20 to 25 ° C. The synthesis of all metal compounds and the preparation of experiments were carried out under a dry nitrogen atmosphere using dry box technology or using dry glass apparatus.

Example  1: 1,2,3,4- tetrahydro -8-((1,2,3,4- tetrahydroquinolin Synthesis of -8-yl) (phenyl) phosphino) quinoline (14)

1,2,3,4-tetrahydroquinoline (13) (1.0 g, 7.51 mmol) was dissolved in ether (20 mL) at room temperature and then n-BuLi (0.53 g, 8.26 mmol) was added at -40 ° C. After stirring at room temperature for 5 hours, CO ₂ was injected at -20 ° C. The temperature was slowly raised to room temperature while CO ₂ was vented and THF (0.81 g, 11.26 mmol) was injected at room temperature. T-BuLi (0.63 g, 9.76 mmol) was injected at −40 ° C., stirred at −20 ° C. for 5 hours, and then slowly injected with p, p-Dichlorophenylphosphine (0.67 g, 3.75 mmol) at −20 ° C. After stirring at room temperature overnight, the solvent was removed and NH ₄ Cl was added. The organic layer was extracted using dichloromethane and water, water was removed with MgSO 4 and the solid was filtered. The filtrate was concentrated and then separated by column chromatography to give a pale yellow solid product (369 mg, 26.4%).

1 H NMR (500 MHz, CDCl 3): 7.45-7.41 (m, 2H), 7.09-6.93 (m, 5H), 6.84 (d, J = 7.5 Hz, 2H), 6.53 (t, 2H), 4.71 (d, J = 6.5 Hz, 2H), 2.82-2.79 (m, 4H), 2.51-2.48 (m, 4H), 1.54-1.49 (m, 4H).

Example  2: 1,2,3,4- tetrahydro -8-((1,2,3,4- tetrahydroquinolin -8-yl) (phenyl) phosphino) quinoline Zirconiumbenzyl  Synthesis of 15

Compound (14) (50 mg, 0.134 mmol) prepared in Example 1 and tetrabenzyl zirconium (ZnBn ₄ , 61 mg, 0.134 mmol) were injected into toluene (5 mL) at −30 ° C. The solids injected into the toluene were all dissolved at room temperature, and the structure was confirmed by NMR.

1 H NMR (500 MHz, CDCl ₃ ): 7.28-6.81 (m, 12H), 6.61-6.54 (m, 4H), 6.38-6.25 (m, 4H), 5.66 (t, 1H), 4.29-4.25 (m, 2H), 3.14-3.09 (m, 2H), 2.78 (s, 1H), 2.66-2.61 (m, 2H), 2.51-2.48 (m, 2H), 2.24 (s, 1H), 1.80-1.76 (m, 2H), 1.70-1.67 (m, 2H).

< Experimental Example >

Experimental Example 1 : Reaction yield and Poly  Density Determination of Olefin

(1) The yield of the polyolefin synthesize | combined in the Example and the comparative example was calculated and calculated from the weight of the particle | grains obtained for 10 minutes.

(2) The density of the polyolefin obtained in the Examples and Comparative Examples was prepared by using a 180 ° C. press mold to make a sheet having a thickness of 3 mm and a radius of 2 cm, and then cooling it at 10 ° C./min on a METTLER scale. Measured.

Experimental Example 2 : Measurement of molecular weight and molecular weight distribution

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polyolefins synthesized in Examples and Comparative Examples were measured through a high temperature GPC (PL-GPC220) instrument, and molecular weight distributions (MWD, Mw / Mn) were determined therefrom. Obtained.

Claims (14)

The transition metal compound of Formula 1
[Chemical Formula 1]

In Chemical Formula 1,
R ₁ is substituted or unsubstituted cycloalkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 5 to 60 carbon atoms, substituted or unsubstituted halogen group having 6 to 60 carbon atoms or substituted with halogen. Or an unsubstituted or substituted unsubstituted cycloalkenyl having 5 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylaryl or halogen group having 7 to 60 carbon atoms, unsubstituted or substituted Arylalkyl having 7 to 60 carbon atoms,
Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ and Q ₆ may be the same as or different from each other, and each independently hydrogen, deuterium, halogen, nitrile, acetylene, amine, amide, C 1 to C Alkoxy carbonyl group having 20, alkanoyl group having 1 to 20 carbon atoms, silyl group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 4 to 20 carbon atoms A heterocyclic group of 20, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and at least two of Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ and Q ₆ are connected to each other; May form an aliphatic ring or an aromatic ring,
Cy1 and Cy2 may be the same as or different from each other, and each independently include a nitrogen atom, hydrogen; halogen; An alkyl group having 1 to 20 carbon atoms; And an aliphatic ring having 4 to 10 carbon atoms which is unsubstituted or substituted with one or more functional groups selected from the group consisting of 6 to 20 carbon atoms, and when two or more functional groups are substituted on the aliphatic ring, they are connected to each other to form an aliphatic ring or an aromatic ring. Can form,
M is a transition metal of Groups 3 to 12;
Y ₁ is oxygen, nitrogen, sulfur or phosphorus,
M and Y ₁ are coordinately bonded,
X ₁ and X ₂ may be the same as or different from each other, and each independently halogen, 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 alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms, an alkyl amido group having 1 to 20 carbon atoms, an aryl amido group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms.
The method of claim 1,
A transition metal compound of formula
[Formula 2]

In Chemical Formula 2,
R ₁ is R ₁ is a halogen group substituted or unsubstituted with 1 to 20 carbon atoms in the cycloalkyl, substituted by halogen or unsubstituted C3 5-60 cycloalkyl, a halogen-substituted or unsubstituted C 6 -C 60 aryl, Cycloalkenyl of 5 to 60 carbon atoms unsubstituted or substituted with a halogen group, alkenyl group of 2 to 20 carbon atoms unsubstituted or substituted with a halogen group, alkylaryl or halogen group of 7 to 60 carbon atoms unsubstituted or substituted with a halogen group or Unsubstituted arylalkyl having 7 to 60 carbon atoms,
Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ and Q ₆ may be the same as or different from each other, and each independently hydrogen, deuterium, halogen, nitrile, acetylene, amine, amide, C 1 to C Alkoxy carbonyl group having 20, alkanoyl group having 1 to 20 carbon atoms, silyl group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 4 to 20 carbon atoms A heterocyclic group of 20, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and at least two of Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ and Q ₆ are connected to each other; May form an aliphatic ring or an aromatic ring,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and having 6 to 20 carbon atoms. An allyl group, an alkylaryl having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms,
M is a transition metal of Groups 3 to 12;
Y ₁ is oxygen, nitrogen, sulfur or phosphorus,
M and Y ₁ are coordinately bonded,
X ₁ and X ₂ may be the same as or different from each other, and each independently halogen, 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 alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms, an alkyl amido group having 1 to 20 carbon atoms, an aryl amido group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms.
The method of claim 1,
A transition metal compound of formula
[Formula 3]

In Chemical Formula 3,
R1 is a phenyl group, cyclohexyl group, methyl, ethyl, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group or tert-butyl group,
X ₁ and X ₂ may be the same or different from each other, and each independently halogen, phenyl group, cyclohexyl group, methyl, ethyl, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group or tert- Butyl group.
An organic ligand compound of Formula 5
[Formula 5]

In Chemical Formula 5,
R ₁ is R ₁ is a halogen group substituted or unsubstituted with 1 to 20 carbon atoms in the cycloalkyl, substituted by halogen or unsubstituted C3 5-60 cycloalkyl, a halogen-substituted or unsubstituted C 6 -C 60 aryl, Cycloalkenyl of 5 to 60 carbon atoms unsubstituted or substituted with a halogen group, alkenyl group of 2 to 20 carbon atoms unsubstituted or substituted with a halogen group, alkylaryl or halogen group of 7 to 60 carbon atoms unsubstituted or substituted with a halogen group or Unsubstituted arylalkyl having 7 to 60 carbon atoms,
Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ and Q ₆ may be the same as or different from each other, and each independently hydrogen, deuterium, halogen, nitrile, acetylene, amine, amide, C 1 to C Alkoxy carbonyl group having 20, alkanoyl group having 1 to 20 carbon atoms, silyl group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 4 to 20 carbon atoms A heterocyclic group of 20, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and at least two of Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ and Q ₆ are connected to each other; May form an aliphatic ring or an aromatic ring,
Cy1 and Cy2 may be the same as or different from each other, and each independently include a nitrogen atom, hydrogen; halogen; An alkyl group having 1 to 20 carbon atoms; And an aliphatic ring having 4 to 10 carbon atoms which is unsubstituted or substituted with one or more functional groups selected from the group consisting of 6 to 20 carbon atoms, and when two or more functional groups are substituted on the aliphatic ring, they are connected to each other to form an aliphatic ring or an aromatic ring. Can form,
Y ₁ is oxygen, nitrogen, sulfur or phosphorus.
The method of claim 4, wherein
An organic ligand compound of formula 6
[Formula 6]

In Chemical Formula 4,
R ₁ is R ₁ is a halogen group substituted or unsubstituted with 1 to 20 carbon atoms in the cycloalkyl, substituted by halogen or unsubstituted C3 5-60 cycloalkyl, a halogen-substituted or unsubstituted C 6 -C 60 aryl, Cycloalkenyl of 5 to 60 carbon atoms unsubstituted or substituted with a halogen group, alkenyl group of 2 to 20 carbon atoms unsubstituted or substituted with a halogen group, alkylaryl or halogen group of 7 to 60 carbon atoms unsubstituted or substituted with a halogen group or Unsubstituted arylalkyl having 7 to 60 carbon atoms,
Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ and Q ₆ may be the same as or different from each other, and each independently hydrogen, deuterium, halogen, nitrile, acetylene, amine, amide, C 1 to C Alkoxy carbonyl group having 20, alkanoyl group having 1 to 20 carbon atoms, silyl group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 4 to 20 carbon atoms A heterocyclic group of 20, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and at least two of Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ and Q ₆ are connected to each other; May form an aliphatic ring or an aromatic ring,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and having 6 to 20 carbon atoms. An allyl group, an alkylaryl having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms,
Y ₁ is oxygen, nitrogen, sulfur or phosphorus.
The method of claim 4, wherein
An organic ligand compound of formula
[Formula 7]

In Chemical Formula 7,
R 1 is a phenyl group, a cyclohexyl group, methyl, ethyl, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group or tert-butyl group.
A transition metal catalyst composition comprising the transition metal compound of claim 1.
The method of claim 7, wherein
A transition metal catalyst composition further comprising a promoter.
The method of claim 8,
The cocatalyst is a transition metal catalyst composition comprising one or more selected from the group consisting of compounds of the following formulas (11) to (13):
(11)
^{[LH] + [Z (E} ) 4] - or ^{[L] + [Z (E} ) 4] -
In Chemical Formula 11,
L is a neutral or cationic Lewis acid,
[LH] + or [L] ⁺ is Bronsted acid,
H is a hydrogen atom,
Z is a group 13 element,
E may be the same as or different from each other, and each independently one or more hydrogen atoms are unsubstituted or substituted with a halogen, a hydrocarbyl having 1 to 20 carbon atoms, an alkoxy functional group or a phenoxy functional group, or having 1 to 20 carbon atoms Is an alkyl group of 20,
[Chemical Formula 12]
D (R ₉ ) ₃
In Chemical Formula 12,
D is aluminum or boron,
R ₉ may be the same as or different from each other, and each independently halogen; Hydrocarbon groups having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen,
[Chemical Formula 13]

In Chemical Formula 13,
R ₁₀ may be the same as or different from each other, and each independently a halogen group; Hydrocarbon groups having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen,
a is an integer of 2 or more.
10. The method of claim 9,
Mole number of the transition metal compound of Formula 1: The number of moles of the compound of Formula 11 is 1: 1 to 1:10 transition metal catalyst composition.
10. The method of claim 9,
Number of moles of the transition metal compound of Formula 1: The number of moles of the compound of Formula 12 or 13 is 1: 1 to 1: 5,000 transition metal catalyst composition.
A process for producing a polyolefin comprising polymerizing a olefin monomer in the presence of the transition metal catalyst composition of claim 7.
The method of claim 12,
The olefin monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidene nobodene, phenyl nobodene, vinyl nobodene, dicyclopentadiene, 1,4-butadiene, 1,5- A method for producing a polyolefin comprising at least one member selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.
13. The method of claim 12,
A method for producing a polyolefin in which the polymerization reaction of the olefin monomer is performed at a temperature of 90 ° C or higher.