KR101229076B1 - Transition metal catalysts composition and preparation method of poly-olefin using the same - Google Patents

Abstract

The present invention relates to a transition metal catalyst composition comprising a transition metal compound and a cocatalyst of a specific structure and a method for producing a polyolefin using the transition metal catalyst composition, according to them, it is possible to achieve high reactivity, high molecular weight and broad It is possible to provide a polyolefin having a molecular weight distribution and excellent mechanical properties and processability.

Description

Transition metal catalyst composition and manufacturing method of polyolefin using same TECHNICAL FIELD

The present invention relates to a transition metal catalyst composition and a method for producing a polyolefin using the same, and more particularly, it can realize high reactivity in the synthesis of polyolefin, has a high molecular weight and a wide molecular weight distribution, excellent mechanical properties and processability A transition metal catalyst composition capable of providing a poly olefin and a process for producing a poly olefin using the same.

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 including metallocene compounds of periodic table Group 4 transition metals such as titanium, zirconium, and hafnium have been developed and 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, so when applied to some products, productivity is significantly reduced due to the extruded load, and a large amount of energy is required for processing. Many efforts have been made to control the molecular weight distribution of polyolefins.

In particular, in order to solve the above problems of the metallocene catalyst, a number of transition metal compounds in which a ligand compound including a hetero atom is coordinated have been introduced. Specific examples of the transition metal compound including such a hetero atom include azaferrocene compound having a cyclopentadienyl group containing a nitrogen atom, and a structure in which a functional group such as a dialkylamine is connected to a cyclopentadienyl group as an additional chain. The metallocene compound or the titanium (lV) metallocene compound in which the alkylamine functional group of the ring form like piperidine was introduce | transduced, etc. are mentioned.

However, these transition metal compounds are too low in activity or difficult to produce polyolefins of desired physical properties, so that only a few cases are actually applied in commercial plants. Accordingly, there is still a need for research on metallocene catalysts capable of realizing higher polymerization performance and providing polyolefins with excellent physical properties.

The present invention is to provide a transition metal catalyst composition that can implement a high reactivity in the synthesis of the poly olefin, and can provide a poly olefin having a high molecular weight and a wide molecular weight distribution, excellent mechanical properties and processability.

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

The present invention is a transition metal catalyst compound having a specific structure; And it provides a transition metal catalyst composition comprising a promoter.

In addition, the present invention provides a method for producing a polyolefin comprising the step of polymerizing the olefin monomer in the presence of the transition metal catalyst composition composition.

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

Hereinafter, the meanings of the substituents will be described in detail.

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

Alkylaryl group means an aryl group in which at least one C1-C20 linear or branched alkyl group is introduced, and an arylalkyl means a straight or branched chain in which one or more C6-C20 aryl groups are introduced. It means an alkyl group.

The amino group is meant to include an unsubstituted amino group (-NH ₂ ), an alkyl amino group, an alkenyl amino group and an aryl amino group. The alkyl amino group refers to an amino group introduced with one or more linear or branched alkyl groups having 1 to 20 carbon atoms, specifically, dimethylamino group, diethylamino group, etc., but is not limited thereto. . The alkenyl amino group refers to an amino group in which one or more linear or branched alkenyl groups having 1 to 20 carbon atoms are introduced. The aryl amino group means an amino group having one or more aryl groups having 6 to 20 carbon atoms introduced therein, and specifically, a diphenylamino group, but is not limited thereto.

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

Alkylene group refers to a divalent functional group derived from a linear or branched alkane.

Alkylsilylene group refers to a divalent functional group derived from silane substituted with a linear or branched alkyl group.

Arylene refers to a divalent functional group derived from arene.

According to one embodiment of the invention, the transition metal catalyst compound of Formula 1; And a transition metal catalyst composition comprising a promoter.

 [Formula 1]

In Formula 1, M ¹ and M ² may be the same as or different from each other, and each is a transition metal element of Group 3 to 10; Cp ¹ and Cp ² may be the same as or different from each other, each of which is a substituted or unsubstituted cyclopentadienyl-based functional group, and when two or more substituents are introduced into the cyclopentadienyl-based functional group, a ring may be formed as a bond between substituents , B ¹ is a divalent organic functional group containing an arylene group; X ¹ and X ² may be the same or different from each other, and each is a phenoxy group; Y ¹ and Y ² may be the same as or different from each other, and each of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl having 1 to 20 carbon atoms, Haloalkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, and 7 to 20 carbon atoms Alkylaryl group of 20, Arylsilyl group of 6 to 20 carbon atoms, Silylaryl group of 6 to 20 carbon atoms, Alkoxy group of 1 to 20 carbon atoms, Alkoxy of 1 to 20 carbon atoms An alkyl group, a halogen group, an amino group, or a tetrahydroborate group; a and b may be an integer of 1 to 5 less than the oxidation number of the M ¹ and M ² , respectively.

The present inventors, when using the transition metal catalyst compound of the formula (1) with a certain cocatalyst, not only can exhibit high reactivity in the polyolefin synthesis reaction, but also excellent mechanical properties and processability while having a high molecular weight and a wide molecular weight distribution Experiments confirmed that it can provide a polyolefin indicating the completed the invention.

The characteristic of the transition metal catalyst composition appears to be derived from the chemical structure inherent in the transition metal catalyst compound of Chemical Formula 1. The transition metal catalyst compound of Chemical Formula 1 has a high molecular weight and excellent mechanical properties by having a chemical structure capable of providing a specific functional group, for example, B ^1, etc. around the metal active point to provide their electrons to the central metal. The polyolefin can be provided, and the molecular weight distribution of the polyolefin obtained by having two metal active sites therein can also be easily controlled. Accordingly, using the transition metal catalyst composition, it is possible to obtain a polyolefin having a high molecular weight and a wide molecular weight distribution, for example, a weight average molecular weight of 1,000,000 or more and a molecular weight distribution (M _w / M _n ) of 3.5 or more.

The M ¹ and M ² may each be a metal element of Groups 3 to 10, preferably a Group 4 transition metal, more preferably titanium (Ti), zirconium (Zr) or hafnium (Hf). have.

The Cp ¹ and Cp ² are substituted or unsubstituted cyclopentadienyl functional groups, respectively, and the cyclopentadienyl functional group is a cyclopentadienyl group, an indenyl group, or a fluorenyl group. Can be.

The substituent introduced into the cyclopentadienyl-based functional group is an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. (Aryl), an arylalkyl group having 7 to 20 carbon atoms (Arylalkyl), an alkylaryl group having 7 to 20 carbon atoms (Alkylaryl), an alkylsilyl group having 1 to 20 carbon atoms (Alkylsilyl), a silylalkyl group having 1 to 20 carbon atoms, Arylsilyl group having 6 to 20 carbon atoms (Arylsilyl), silylaryl group having 6 to 20 carbon atoms (Silylaryl), alkoxy group having 1 to 20 carbon atoms (alkoxy), alkylsiloxy group having 1 to 20 carbon atoms (Alkylsiloxy), 6 to 20 carbon atoms At least one substituent selected from the group consisting of an aryloxy group, an halogen group, and an amino group of 20 may be used. In addition, when two or more such substituents are introduced into the cyclopentadienyl-based functional group, a ring may be formed by a bond between the substituents.

The B ¹ may be a divalent organic functional group including an arylene group. Specifically, B ¹ may be an arylene group having 5 to 40 carbon atoms or a divalent functional group represented by Formula 2 below.

(2)

In Formula 2, Ary ¹ and Ary ² may be the same or different from each other, and each may be an arylene-based functional group. In addition, the B ² is an alkylene group having 1 to 20 carbon atoms, an alkylsilylene group having 1 to 20 carbon atoms, a haloalkylene group having 1 to 20 carbon atoms, and a cycloalkyl having 3 to 20 carbon atoms. It may be an alkylene (Cycloalkylene) group, an arylalkylene group of 7 to 20 carbon atoms, an arylsilylene group of 6 to 20 carbon atoms, or an alkylarylene group of 7 to 20 carbon atoms, such a functional group May be substituted with an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen. C may be an integer of 0 to 5.

Specific examples of the arylene-based functional groups used in Ary ¹ and Ary ² may include a phenylene group, a biphenylene group, a terphenylene group, a naphtylene group, and binaphthylene ( Binaphtylene group, Fluorenylene group, Anthracylene group, Pyridylene group, Bipyridylene group, Terpyridylene group, Terpyridylene group, Quinolylene, Pyriylene A pyridazylene group, a pyrimidylene group, a pyrazylene group, a quinoxalylene group, and the like, but are not necessarily limited thereto.

Specific examples of the B ² , a methylene group, a dimethylmethylene group, a diethylmethylene group, a diphenylmethylene group, a tetramethylethylene group, an ethylene group, Tetraethylethylene group, tetraphenylethylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group, cyclohexylene group, Tetrafluoroethylene group, etc., but is not necessarily limited thereto.

X ¹ and X ² may each be a phenoxy functional group, and such a phenoxy functional group includes a compound represented by Formula 3 below.

[Formula 3]

In Formula 3, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, each hydrogen, an alkyl group having 1 to 20 carbon atoms, alkylsilyl having 1 to 20 carbon atoms (Alkylsilyl) ) Group, C1-C20 silylalkyl, C1-C20 haloalkyl group, C3-C20 cycloalkyl group, C6-C20 aryl group, C7 Arylalkyl group having 20 to 20 carbon atoms, alkylaryl group having 7 to 20 carbon atoms, arylsilyl group having 6 to 20 carbon atoms, silylaryl group having 6 to 20 carbon atoms, and 1 to 20 carbon atoms An alkoxy group, an alkylsiloxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a halogen group or an amino group, and the benzene ring When substituted with two or more functional groups, R ¹ , R ² , R ³ , R ⁴ and R ⁵ Two or more of them may be joined to form a ring.

The Y ¹ and Y ² may be the same or different from each other, and hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, and a silylalkyl having 1 to 20 carbon atoms, respectively. , A haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and 7 carbon atoms Alkylaryl group of 20 to 20, arylsilyl group of 6 to 20 carbon atoms, Silylaryl group of 6 to 20 carbon atoms, alkoxy group of 1 to 20 carbon atoms, of 1 to 20 carbon atoms It may be an alkylsiloxy group, a halogen group, a halogen group, an amino group, or a tetrahydroborate group.

Wherein a and b can be an integer of the M ¹ and is a number determined by the oxidation number of M ^2, wherein M ¹ and M ² 1 to 2 smaller than the oxidation number of 5 each.

Meanwhile, the transition metal catalyst compound may include a cocatalyst, and specific examples of the cocatalyst may include compounds of the following Chemical Formulas 4 to 6.

[Formula 4]

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

In Formula 4, 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, E is the same or different Each independently substituted or unsubstituted with one or more functional groups selected from the group consisting of halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxy functional group and phenoxy functional group It may be an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms.

The compound of Formula 4 may play a role of activating the transition metal catalyst 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 compound, the number of moles of the transition metal catalyst compound of Formula 1: The number of moles of the compound of Formula 4 may be 1: 1 to 1:10. 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.

As a specific example of the compound of Formula 4, in the case of trialkylammonium salt, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluoro Phenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (2-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluoro Rophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4-triisopropylsilyl) -2,3,5, 6-tetrafluorophenyl) borate, N, N-dimethyla Linium pentafluorophenoxycitries (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (Pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri Propylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl ) Ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-di Ethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluoro Phenyl Borate, decyldimethylammonium tetrakis (pentafluorophenyl) borate, dodecyldimethylammonium tetrakis (pentafluorophenyl) borate, tetradecyldimethylammonium tetrakis (pentafluorophenyl) borate, hexadecyldimethylammonium tetrakis (Pentafluorophenyl) borate, octadecyldimethylammonium tetrakis (pentafluorophenyl) borate, eicosyldimethylammonium tetrakis (pentafluorophenyl) borate, methyldidecylammonium tetrakis (pentafluorophenyl) borate, Methyldidodecylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentafluorophenyl) borate, methyldihexadecylammonium tetrakis (pentafluorophenyl) borate, methyldioctadecylammonium tetra Kis (pentafluorophenyl) borate, methyldiecosylammonium tetrakis (pen Fluorophenyl) borate, tridecylammonium tetrakis (pentafluorophenyl) borate, tridodecylammonium tetrakis (pentafluorophenyl) borate, tritetradecylammonium tetrakis (pentafluorophenyl) borate, trihexadecyl Ammonium tetrakis (pentafluorophenyl) borate, trioctadecylammonium tetrakis (pentafluorophenyl) borate, triicosylammonium tetrakis (pentafluorophenyl) borate, decyldi (n-butyl) ammonium tetrakis ( Pentafluorophenyl) borate, dodecyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, octadecyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-didodecyl Anilinium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecylanilinium tetrakis (pentafluorophenyl) borate, methyldi (dodecyl) ammonium tetra Scan it may be mentioned (pentafluorophenyl) borate and the like.

Moreover, in the case of a dialkyl ammonium salt, di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, dicyclohexyl ammonium tetrakis (pentafluorophenyl) borate, etc. are mentioned.

Moreover, in the case of a carbonium salt, trophylium tetrakis (pentafluorophenyl) borate, triphenylmethyllium tetrakis (pentafluorophenyl) borate, benzene (diazonium) tetrakis (pentafluorophenyl) borate, etc. are mentioned. Can be.

In particular, preferred examples of the compound of Formula 4 include N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, di (octadecyl) methylammonium tetrakis (Pentafluorophenyl) borate, di (octadecyl) (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylmethyllium tetrakis (pentafluorophenyl) borate, trophylium tetrakis (pentafluoro Rophenyl) borate etc. are mentioned.

On the other hand, the promoter may include a compound of formula (5).

 [Formula 5]

D ( R ₉ ) ₃

In Formula 5, D is aluminum or boron, R ₉ may be the same or different from each other, and each independently halogen; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with halogen; An aryl group of 6 to 20 carbon atoms unsubstituted or substituted with halogen; It may be an alkylaryl group having 7 to 20 carbon atoms unsubstituted or substituted with halogen or an alkoxy group having 1 to 20 carbon atoms substituted or unsubstituted with halogen.

In addition, the promoter may include a compound represented by the following formula (6).

 [Formula 6]

In Formula 6, R ₁₀ may be the same as or different from each other, and each independently a halogen group; An alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with halogen, and a may be an integer of 2 or more.

The compound of Formula 5 or 6 may serve as a scavenger to remove impurities that act as poisons to the catalyst in the reactants.

In the transition metal catalyst composition, the number of moles of the transition metal catalyst compound of Formula 1: The number of moles of the compound of Formula 5 may be 1: 1 to 1:10, the number of moles of the transition metal catalyst compound of Formula 1: The molar number of the compound of formula 6 may be 1: 1 to 1:10 ⁶ . If the amount of the compound of Formula 5 or 6 is used in a very small amount, the effect of the addition of scavenger is insignificant, and if used in an excessive amount, the excess alkyl group, which does not participate in the reaction, rather inhibits the catalytic reaction, and thus, the catalyst poison. As a result, a side reaction may proceed to cause an excessive amount of aluminum or boron to remain in the polymer.

Specific examples of the compound of Formula 5 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, dimethylaluminum methoxide (Dimethylaluminum methoxide), diethylaluminum methoxide (Diethylaluminum methoxide), dibutylaluminum methoxide, Methylaluminum di methoxide, ethylaluminum dimethoxide, butylaluminum dimethoxide, butylaluminum dimethoxide, dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, methyl Aluminum dichloride (Methylaluminum dichloride), ethyl aluminum dichloride (Ethylaluminum dichloride), butyl aluminum dichloride (Butylaluminum dichloride) and the like, preferably trimethyl aluminum, triethyl aluminum or triisobutyl aluminum can be used.

Specific examples of the compound of Formula 6 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, hexyl aluminoxane (Hexylaluminoxane), octyl aluminoxane (Octylaluminoxane), decyl aluminoxane (Decylaluminoxane) and the like. Preferably, methyl aluminoxane is mentioned.

On the other hand, the transition metal catalyst composition may be used in a fixed state on the carrier. An organic / inorganic compound having a fine pore on the surface of the carrier and having a large surface area can be used without particular limitation. Magnesium, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide, thorium oxide or mixtures thereof may be used alone or in combination of two or more thereof. Specific examples of the mixture include SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -CrO ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, and the like. Can be.

When the transition metal catalyst composition is immobilized on a carrier, a method of directly supporting a transition metal catalyst compound (Formula 1) synthesized on a dehydrated carrier (Support), pretreatment of the carrier with a promoter and then transition A method of supporting a metal compound, a method of treating a cocatalyst after supporting a transition metal compound synthesized on a carrier, a method of reacting a transition metal compound with a promoter and then reacting with a carrier, and the like can be used.

When the metal catalyst composition is fixed to a carrier, butane (Butane), pentane (Pentane), normal hexane (Hexane), heptane (Heptane), Octane (Nonane), Decane (Decane), Undecane Aliphatic hydrocarbon solvents such as Undecane and Dodecane or aromatic hydrocarbons such as Benzene, Monochlorobenzene, Dichlorobenzene, Trichlorobenzene and Toluene There are halogenated aliphatic hydrocarbon solvents such as solvent, dichloromethane, trichloromethane, dichloroethane, trichloroethane, etc., and they can be used alone or in combination of two or more during the supporting reaction. .

The temperature at which the catalyst composition is fixed to the carrier may be 0 ° C to 120 ° C, preferably 20 ° C to 100 ° C.

On the other hand, the transition metal catalyst composition may further include a solvent, wherein the type of the solvent is not limited to a large amount, a solvent known to be commonly used in the synthesis of polyolefins, for example butane (Butane), pentane ( Aliphatic hydrocarbon solvents such as Pentane, Hexane, Heptane, Octane, Nonane, Decane, Uncane, Undecane and Dodecane; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene; Or halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane, and trichloroethane.

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

By using the transition metal catalyst compound, not only can exhibit high reactivity in the polyolefin polymerization reaction, but also have a high molecular weight and a wide molecular weight distribution can provide a polyolefin having excellent mechanical properties and processability.

Details of the transition metal catalyst compound are as described above.

The polymerization of the olefin monomer may be carried out in a slurry phase, a liquid phase, a gas phase, a bulk phase, and the polymerization reaction is performed in a liquid phase or a slurry phase. , Solvent (Solvent) or monomer (Monomer) itself can be used as a medium, and the monomer used in the polymerization can be used alone or a mixture of two or more kinds. At this time, the solvent used is as described above.

The temperature applied to the polymerization reaction of the olefin monomer is not particularly limited, but if the polymerization reaction temperature is too low, the reactivity of the olefin monomer is not high, it may be difficult to synthesize polyolefin, if the polymerization reaction temperature is too high olefin monomer Since it can be thermally decomposed, it is preferable to proceed with the polymerization reaction at -50 to 200 ℃, preferably 0 to 150 ℃. The temperature of the polymerization reaction can be carried out at 1.0 to 1,000 atm, preferably 2 to 200 atm.

The amount of the transition metal catalyst composition used in the polymerization reaction step may be appropriately adjusted in consideration of the reaction conditions, the physical properties of the polyolefin to be prepared, etc., but the concentration of the central metal in the reaction system 10 ^-8 mol / liter to 1 mol / liter Is suitable, and may be preferably used in the range of 10 ⁻⁷ mol / liter to 10 ⁻² mol / liter.

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.

When the olefin monomer is polymerized in the presence of the transition metal catalyst composition, a polymer or copolymer having a weight average molecular weight of 1,000,000 or more and a molecular weight distribution (M _w / M _n ) of 3.5 or more may be synthesized.

According to the present invention, there can be provided a transition metal compound, a transition metal catalyst composition and a method for producing a poly olefin that can implement high reactivity, can provide a polyolefin having a wide molecular weight distribution and excellent mechanical properties and processability.

The invention is explained in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

Synthetic example Organic Ligand  Synthesis of Compounds and Transition Metal Compounds

The following synthesis reaction was carried out in an Inert Atmosphere such as Nitrogen or Argon, using a Standard Schlenk technique and a Glove Box technique.

Tetrahydrofuran (THF), Toluene, n-hexane (n-Hexane), n-Pentane, Diethyl ether, Methylene chloride (Methylene chloride, CH ₂ Cl ₂ Synthetic solvent (Solvent), etc.) was used while removing the water by passing through an activated alumina layer (Activated Alumina Column) and then stored on an activated molecular sieve (Molecular Sieve 5A, Yakuri Pure ChemicalsCo). The double hydrogen substituted chloroform (CDCl ₃ ) used in the analysis of the organometallic compound was used by drying on an activated molecular sieve (Molecular Sieve 5A).

4,4'-Dibromobiphenyl, 2,3,4,5-tetramethylcyclopenta-2-enone (2,3,4,5-Tetramethyl-cyclopent-2-enone ), 2,6-Diisopropylphenol (2,6-Diisopropylphenol), n-Butyllithium, 2.5M solution in n-Hexane, para-Toluenesulfonic acid monohydrate (p-TsOH H ₂ O)), Trimethylsilyl chloride (Trimethylsilyl chloride, Me ₃ SiCl (TMSCl)), Triisopropoxytitanium chloride (ClTi (OiPr) ₃ ), etc. were purchased and used without further purification. 1,2-bis (4-bromophenyl) ethane (1,2-Bis (4-Bromophenyl) ethane) and 3,4-dimethylsiglopenta-2-enone (3,4-Dimethylcyclopent-2-enone ) Was synthesized according to the method described in the literature.

¹ H NMR and ¹³ C NMR were measured using a Bruker Avance 400 Spectrometer at room temperature, and elemental analysis was measured using EA 1110-FISION (CE Instruments).

[ Synthetic example  1] 4,4'- Biphenylene  Bis {(2,3,4,5- Tetramethylcyclopentadienyl ) (D-2,6- Diisopropylphenoxytitanium Dichloride )} (4,4 '-( C ₆ H ₄ ) ₂ {( C ₅ Me ₄ ) [Ti (O-2,6- i Pr ₂ Ph) Cl ₂ ]} ₂ ) Synthesis of

< Synthetic example  1-1: 4,4'- Vis (2,3,4,5- Tetramethylcyclopentadienyl ) Biphenylene  (4,4 '-(C ₅ Me ₄ H) ₂ (C ₆ H ₄ ) ₂ Synthesis of)

9.36 g (30 mmol) of 4,4'-dibromobiphenyl was slurried in 40 ml of diethyl ether and then 2 equivalents of 24 mL of n-butyllithium was added at -30 ° C. The reaction solution was heated up to 0 ° C., and the reaction solution became clear as the temperature was increased.

Then, it is confirmed that a precipitate (4,4'-Biphenyl dilithium salt) is produced. After further stirring at this temperature for 30 minutes, the reaction solution is heated to room temperature and stirred for two more hours until the formation of precipitation stops. The precipitate was allowed to settle and then the supernatant was removed and 30 ml of tetrahydrofuran was added thereto.

Then, the reaction solution was cooled to −78 ° C., and then a solution obtained by dissolving 8.29 g of 2,3,4,5-tetramethylcyclopenta-2-enone in 20 mL tetrahydrofuran was slowly added thereto. Thereafter, the temperature was raised to room temperature, stirred for 12 hours, and 30 ml of saturated ammonium chloride (NH 4 Cl) solution was added to terminate the reaction.

The resulting organic solution layer and the water layer were separated, and then the water layer was further extracted with 100 mL of diethyl ether, and the diethyl ether layer was combined with the previously separated organic solution layer. The combined organic solution layers were removed with excess water using anhydrous magnesium sulfate (MgSO ₄ ), and then the solid material was filtered off and dried under vacuum to give a colorless oily reaction product. The obtained reaction product was no longer purified and dissolved in 30 ml of methylene chloride at room temperature, and then 0.1 g of a catalytic amount of p-toluenesulfonic acid hydrate was added in a solid state. After further stirring for 1 hour, most of the methylene chloride was removed in vacuo. To this was added 30 ml of n-hexane. The resulting pale yellow solid was obtained by filtration through a glass filter, which was washed with 30 ml of ethanol, 30 ml of diethyl ether and 30 ml of n-pentane in this order, followed by vacuum drying to obtain 7.50 g of title. The compound was obtained in 63% yield.

NMR data of the title compound produced were as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.61 (d, 4H), 7.30 (d, 4H), 3.22 (q, 2H), 2.08 (s, 6H), 1.94 (s, 6H), 1.87 (s , 6H), 0.99 (s, 6H) ppm.

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 142.3, 140.9, 137.8, 137.5, 135.8, 135.2, 128.7, 126.5, 50.0, 14.9, 12.9, 12.0, 11.1 ppm.

< Synthesis Example 1 -2: 4,4'- Biphenylene  Bis {(2,3,4,5- Tetramethylcyclopentadienyl ) titanium Trichloride } (4,4 '-( C ₆ H ₄ ) ₂  {( C ₅ Me ₄ ) TiCl ₃ } ₂ Synthesis of)

1.97 g (5.0 mmol) of 4,4'-bis (2,3,4,5-tetramethylcyclopentadienyl) biphenylene obtained in Synthesis Example 1-1 was prepared in two equivalents of n-butyllithium ( 4.0 ml) to give 4,4'-bis (2,3,4,5-tetramethylcyclopentadienyl) biphenylene dilithium salt, which is slurried over 20 mL tetrahydrofuran Then, it was added to a 20 ml solution of tetrahydrofuran containing 2 equivalents of triisopropoxytitanium chloride (ClTi (OiPr) ₃ , 2.61 g) at 0 ° C.

The reaction solution was raised to room temperature, and then stirred for 24 hours. Tetrahydrofuran was then completely removed and 30 ml of methylene chloride was added to dissolve the reaction product. The reaction product dissolved in methylene chloride was filtered through a layer of celite to remove solids produced as a by-product of the reaction to give a pale green solution. An excess of trimethylsilylchloride ((CH ₃ ) ₃ SiCl, 3 equiv, 11.5 ml) was added to the pale green solution at 0 ° C.

In addition, the reaction solution was heated to room temperature and then stirred. At this time, it was observed that the red precipitate gradually formed as the reaction proceeded. After stirring for 12 hours, the red solid remained barely wetted with methylene chloride, washed twice with 20 ml of n -hexane / diethyl ether (v / v = 2/1) and dried under vacuum to give a scarlet color. 2.23 g of the title compound in fine crystal form were obtained in 65% yield.

NMR data of the title compound produced were as follows.

¹ H NMR (400.13 MHz, CDCl 3): δ 7.70 (d, 4H), 7.46 (d, 4H), 2.51 (s, 12H), 2.44 (s, 12H) ppm.

Anal. Calcd for C ₃₀ H ₃₂ Cl ₆ Ti ₂ : C, 51.40; H, 4.60. Found: C, 51.14; H, 4.92.

< Synthesis Example 1 -3: 4,4'- Biphenylene  Bis {(2,3,4,5- Tetramethylcyclopentadienyl ) (D-2,6- Diisopropylphenoxytitanium Dichloride )} (4,4 '-( C ₆ H ₄ ) ₂ {( C ₅ Me ₄ ) [Ti (O-2,6- i Pr ₂ Ph) Cl ₂ ]} ₂ Synthesis of)

0.351 g (0.5 mmol) and 2 equivalents of 4,4'-biphenylene bis {(2,3,4,5-tetramethylcyclopentadienyl) titanium trichloride} synthesized in Synthesis Example 1-2 0.184 g of lithium salt of 2,6-diisopropylphenol (LiO-2,6- i Pr ₂ Ph) of was added to the same reactor, and 20 ml of tetrahydrofuran was added at -78 ° C.

The reaction solution was slowly warmed up to room temperature and then further stirred at room temperature for 6 hours. After the tetrahydrofuran was removed from the reaction solution, the reaction product was extracted with methylene chloride, filtered through the celite pad to remove the reaction byproduct, and then volatilized until 10 ml of methylene chloride remained. 20 mL of n -hexane was added to the condensed solution to form a layer, and then stored at −20 ° C. to obtain 0.271 g of the title compound as red crystals in 55% yield.

NMR data of the title compound produced were as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.66-7.58 (m, 8H), 7.01-6.98 (m, 6H), 3.03 (sept, 4H), 2.33 (s, 12H), 2.28 (s, 12H) , 1.04 (d, 24H) ppm.

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 159.9, 139.9, 139.6, 136.2, 133.6, 132.3, 131.1, 130.9, 126.8, 123.6, 123.2, 26.8, 23.8, 14.0, 13.3 ppm.

Anal. Calcd for C ₅₄ H ₆₆ Cl ₄ O ₂ Ti ₂ : C, 65.87; H, 6.76. Found: C, 66.14; H, 7.27.

[ Synthetic example  2] 1,2-bis [4-{(2,3,4,5- Tetramethylcyclopentadienyl ) Di- (2,6- Diisopropylphenoxy )titanium Dichloride } Phenyl ] Ethane ((1,2- [4-{( C ₅ Me ₄ ) Ti (O-2,6- i Pr ₂ Ph) Cl ₂ } C ₆ H ₄ ] ₂ (CH ₂ CH ₂ ))

< Synthesis Example 2 -1: 1,2- Vis -[4- (2,3,4,5- Tetramethylcyclopentadienyl ) Phenyl ] Ethane (1,2- [4- (C ₅ Me ₄ H) C ₆ H ₄ ] ₂ (CH ₂ CH ₂ Synthesis of))

1,2-di- (4-bromophenyl) ethane (40 mmol, 13.602 g) was dissolved in 50 ml of diethyl ether, cooled to 0 ° C., and 2.1 equivalents of n -butyllithium (33.6 ml) were injected into the syringe. Drop by drop was added. Then, the reaction solution was stirred at 0 ° C. for 1 hour, and the temperature was slowly raised to room temperature and further stirred for 2 hours, at which time a white precipitate was formed.

The precipitate was allowed to settle and the portion of the upper solution was decanted and the precipitate was dissolved in 30 ml of tetrahydrofuran while maintaining -78 ° C. In another flask prepared, 2,3,4,5-tetramethylcyclopenta-2-enone (80 mmol, 11.057 g) was dissolved in 20 ml of tetrahydrofuran, and this solution was dissolved in the previous precipitation solution using a cannula. Slowly dropwise added. When the temperature was slowly raised to room temperature and stirred for 6 hours or more, a pale yellow solution was formed.

An appropriate amount of saturated aqueous ammonium chloride solution was added to the reaction solution, and the organic layer was extracted with 50 ml (X3) of diethyl ether, and the mixture was dried over anhydrous magnesium sulfate and filtered. The solvent was removed from the rotary evaporator to obtain a yellow sticky oil. The oil was dissolved in 50 ml of dichloromethane, and a catalytic amount of paratoluenesulfonic acid hydrate (0.1 g) was added thereto, followed by stirring at room temperature for 2 hours. After stirring the solvent was removed using a rotary evaporator and the solid material obtained was washed with 30 ml of hexane and filtered off. The filtered yellow solid was washed with 30 ml of anhydrous ethanol (X3), 30 ml of diethyl ether, 30 ml of n -pentane and dried in vacuo to give 7.608 g of a pale yellow solid in 45% yield.

The NMR data of the obtained compound was as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.18 (m, 8H), 3.17 (q, 2H), 2.93 (m, 4H), 2.02 (s, 6H), 1.91 (s, 6H), 1.85 (s , 6H), 0.95 (d, 6H) ppm.

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 142.7, 140.4, 139.0, 136.7, 135.0, 134.8, 128.4, 128.1, 50.1, 37.6, 14.9, 12.7, 11.9, 11.1 ppm.

< Synthesis Example 2 -2: 1,2- [4-{( C5Me ₄ ) ( TiCl ₃ )} ₂ ( C ₆ H ₄ )] ₂ ( CH ₂ CH ₂ ) 1,2-bis [4-{(2,3,4,5-tetramethylcyclopentadienyl) ( Titanium trichloride )} Phenyl ] Synthesis of Ethane>

2.113 g (5.0 mmol) of 1,2-bis- [4- (2,3,4,5-tetramethylcyclopentadienyl) phenyl] ethane obtained in Synthesis Example 2-1 was synthesized above. Proceed in the same manner as in the red fine crystal form of 1.896 g of the title compound was obtained in 52% yield.

The NMR data of the obtained compound was as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.24 (m, 8H), 2.99 (s, 4H), 2.46 (s, 12H) 2.41 (s, 12H) ppm.

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 142.9, 142.0, 138.7, 136.1, 130.8, 130.3, 128.4, 37.3, 15.5, 14.6 ppm.

Anal. Calcd for C ₃₂ H ₃₆ Cl ₆ Ti ₂ : C, 52.72; H, 4.98. Found: C, 52.65; H, 5.44.

< Synthesis Example 2 -3: 1,2-bis [4-{(2,3,4,5- Tetramethylcyclopentadienyl ) Di- (2,6- Diisopropylphenoxy )titanium Dichloride } Phenyl ] Ethane ((1,2- [4-{( C ₅ Me ₄ ) Ti (O-2,6- i Pr ₂ Ph) Cl ₂ } C ₆ H ₄ ] ₂ (CH ₂ CH ₂ Synthesis of))

1,2-bis [4-{(2,3,4,5-tetramethylcyclopentadienyl) (titanium trichloride)} phenyl] ethane obtained in Synthesis Example 2-2 0.729 g (1.0 mmol) was synthesized in the same manner as in Synthesis Example 1-3 to obtain 0.405 g of the title compound as a dark red fine crystal in 40% yield.

The NMR data of the obtained compound was as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.42 (d, 4H), 7.25 (d, 4H), 7.01 to 6.95 (m, 6H), 3.03 (sept, 4H), 2.96 (s, 4H), 2.28 (s, 12H) 2.24 (s, 12H), 1.04 (d, 24H) ppm.

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 159.8, 142.1, 139.6, 137.0, 133.3, 131.1, 130.8, 130.6, 128.2, 123.5, 123.1, 37.4, 26.7, 23.8, 14.0, 13.2 ppm.

Anal. Calcd for C ₅₆ H ₇₀ Cl ₄ O ₂ Ti ₂ : C, 66.42; H, 6.97. Found: C, 66.11; H, 6.73.

[ Synthetic example  3] 1,2-bis [4-{(3,4,- Dimethylcyclopentadienyl ) Di- (2,6- Diisopropylphenoxy )titanium Dichloride } Phenyl ] Ethane ((1,2- [4-{( C ₅ Me ₂ H ₂ ) Ti (O-2,6- i Pr ₂ Ph) Cl ₂ } C ₆ H ₄ ] ₂ (CH ₂ CH ₂ ))

< Synthesis Example 3 -1: 1,2- Vis -[4- (3,4- Dimethylcyclopentadienyl ) Phenyl ] Ethane (1,2- [4- (3,4-C) ₅ Me ₂ H ₃ ) C ₆ H ₄ ] ₂ ( CH ₂ CH ₂ Synthesis of))

Except for using 3,4-dimethyl-2-cyclopentenone (80 mmol, 8.732 g) instead of using 2,3,4,5-tetramethylcyclopenta-2-enone in Synthesis Example 2-1 The same procedure was followed to obtain 9.53 g of an ivory-colored solid in 65% yield.

The NMR data of the obtained compound was as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.35 (d, 4H), 7.09 (d, 4H), 6.60 (s, 2H), 3.24 (s, 4H), 2.86 (s, 4H), 1.96 (s , 6H), 1.87 (s, 6H) ppm.

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 142.4, 139.7, 135.5, 135.4, 134.2, 131.0, 128.6, 124.5, 45.3, 37.6, 13.4, 12.6 ppm.

< Synthesis Example 3 -2: 1,2-bis [4-{(3,4- Dimethylcyclopentadienyl ) ( Titanium trichloride )} Phenyl ] Ethane ([1,2- [4-{( C ₅ Me ₂ H ₂ ) ( TiCl ₃ )} ₂ ( C ₆ H ₄ )] ₂ ( CH ₂ CH ₂ ) Synthesis of

In the same manner as in Synthesis Example 1-2, 1.833 g (5.0 mmol) of 1,2-bis- [4- (3,4-dimethylcyclopentadienyl) phenyl] ethane obtained in Synthesis Example 3-1 From 2.255 g of the title compound was obtained in 67% yield as a dark red solid.

The NMR data of the obtained compound was as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.57 (d, 4H), 7.17 (s, 4H), 7.10 (d, 4H), 2.93 (s, 4H), 2.47 (s, 12H) ppm.

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 143.3, 140.6, 139.3, 130.8, 129.2, 126.1, 119.1, 37.4, 16.0 ppm.

Anal. Calcd for C ₂₈ H ₂₈ Cl ₆ Ti ₂ : C, 49.97; H, 4.19. Found: C, 49.60; H, 5.02.

< Synthesis Example 3 -3: 1,2-bis [4-{(3,4,- Dimethylcyclopentadienyl ) Di- (2,6- Diisopropylphenoxy )titanium Dichloride } Phenyl ] Ethane ((1,2- [4-{( C ₅ Me ₂ H ₂ ) Ti (O-2,6- i Pr ₂ Ph) Cl ₂ } C ₆ H ₄ ] ₂ (CH ₂ CH ₂ ))

0.673 g (1.0 mmol) of 1,2-bis [4-{(3,4-dimethylcyclopentadienyl) (titanium trichloride)} phenyl] ethane obtained in Synthesis Example 3-2 was synthesized above. Synthesis was carried out in the same manner as in to obtain 0.526 g of the title compound in the form of dark red fine crystals in 55% yield.

The NMR data of the obtained compound was as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.26 (d, 4H), 7.00 (d, 4H), 6.95 (m, 6H), 6.71 (s, 4H), 2.78 (s, 4H), 2.76 (sept , 4H), 2.42 (s, 12H), 1.02 (d, 24H) ppm.

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 162.8, 142.4, 138.8, 135.5, 134.8, 129.6, 128.6, 125.5, 123.8, 122.8, 116.0, 37.2, 26.9, 23.5, 15.00 ppm.

Manufacturing example : Preparation of Supported Catalyst

All of the following synthesis reactions were conducted in an inert atmosphere such as nitrogen or argon, using standard Schlenk technology and glove box technology.

Toluene was purchased from Sigma-Aldrich and then further dried by passing through an activated molecular sieve (4A) or activated alumina layer, followed by methylaluminoxane ( Methylaluminoxane (MAO) was purchased from Albemarle's 10% toluene solution and used without further treatment. Silica used Grace XPO2412 without further treatment and biscyclopentadienylzirconium dichloride (Cp2ZrCl2) was purchased from Strem and used without further treatment.

< Manufacturing example  1: Preparation of Supported Catalysts>

In the Glove Box, the catalyst of Synthesis Example 2-3 (0.038g, 37.5umol) was taken out of the Glove Box in a 100ml Schlenk Flask, and methylaluminoxane (MAO, 5.1ml, 7.5mmol) was added at 10 ° C. Slowly added. The reaction solution was then stirred at 10 ° C. for 10 minutes and then further stirred at 25 ° C. for 60 minutes. Another 100 ml Schlenk flask was filled with Silica (0.5 g) in a Glove Box, and then slowly added to the reaction solution at 0 ° C. Thereafter, the mixture was stirred at 0 ° C. for about 1 hour, heated to 65 ° C. for 1 hour, cooled to 25 ° C., and stirred for 12 hours.

The reaction product thus obtained was dried in vacuo to obtain 0.9 g of a supported catalyst for free flowing.

< Preparation Example 2 : Preparation of Supported Catalysts>

0.9 g of the supported catalyst was obtained in the same manner as in Preparation Example 1, except that the catalyst of Synthesis Example 3-3 (0.036 g, 37.5 umol) was used instead of the catalyst of Synthesis Example 2-3.

< Production Example 3 : Preparation of Supported Catalysts>

Supported catalyst 0.85 in the same manner as in Preparation Example 1, except that a catalyst of biscyclopentadienylzirconium dichloride (Cp ₂ ZrCl ₂ ) (0.022 g, 75.0 umol) was used instead of the catalyst of Synthesis Example 2-3. g was obtained.

Example  And Comparative example : Poly  Synthesis of Olefin

The following polymerization process is carried out while maintaining a constant ethylene pressure after injecting the required amount of methylaluminoxane, triisobutylaluminum, transition metal compound or supported catalyst in an autoclave completely isolated from outside air. It became.

Normal hexane ( n- Hexane), toluene, etc. used in the polymerization can be purchased from Sigma-Aldrich, Anhydrous Grade, and then activated molecular sieve (4A) or activated alumina (Alumina). After passing through the layer), it was further dried and used. Hydrochloric acid (HCl, 35%) and methanol (MeOH) were used as reagent grades in Samjeon Chem.

The molecular weight and molecular weight distribution of the polymer produced after polymerization were measured by GPC (Gel Permeation Chromatography, PL-GPC220) method, and melting point was measured by DSC (Differential Scanning Calorimetry, TA Instruments) method.

< Example 1 : Unsupported  With catalyst Poly  Synthesis of Olefin>

After replacing the inside of stainless steel high pressure reactor with internal capacity of 2L at room temperature with nitrogen, 1L of normal hexane was filled, and 15mmol (10ml) of methylaluminoxane (MAO, Albemarle 10%) was added based on Al atom. , And a solution (2 ml, 7.5 umol) in which the transition metal compound of Synthesis Example 2-3 was dissolved in toluene was injected.

Thereafter, the reaction solution was heated up to 60 ° C, and ethylene gas was injected to carry out the polymerization reaction for 1 hour while maintaining the temperature of 70 ° C and the total pressure of 6 bar.g. 50 ml of 10% HCl / MeOH was added to terminate the polymerization reaction, and the resulting polymer was washed with excess methanol and dried under vacuum at 60 ° C. for 15 hours.

< Comparative Example 1 : Unsupported  With catalyst Poly  Synthesis of Olefin>

A polyolefin was synthesized by performing a polymerization reaction in the same manner as in Example 1, except that biscyclopentadienyl zirconium dichloride (2 ml, 15 μol) was used instead of the transition metal compound of Synthesis Example 2-3.

< Example 2 : Supported catalyst Poly  Synthesis of Olefin>

After replacing the inside of the stainless steel autoclave having an internal capacity of 2 L with nitrogen, 1 L of normal hexane was charged, and 2 mmol of triisobutylaluminum and 0.1 g of the supported catalyst synthesized in Preparation Example 1 were sequentially injected. .

Thereafter, the reaction solution was heated up to 60 ° C, ethylene gas was injected, and the polymerization reaction was performed for 1 hour while maintaining the temperature of 70 ° C and the total pressure of 7 bar.g. 50 ml of 10% HCl / MeOH was added to terminate the polymerization reaction, and the resulting polymer was washed with excess methanol and dried under vacuum at 60 ° C. for 15 hours.

< Example 3 : Supported catalyst Poly  Synthesis of Olefin>

A polyolefin was synthesized by the polymerization reaction in the same manner as in Example 2, except that 0.1 g of the supported catalyst synthesized in Preparation Example 2 was used.

< Comparative Example 2 : Supported catalyst Poly  Synthesis of Olefin>

A polyolefin was synthesized by the polymerization reaction in the same manner as in Example 2, except that 0.1 g of the supported catalyst synthesized in Preparation Example 3 was used.

< Example  And In a comparative example  Result of Polymerization>

Measurement results of the polyolefin synthesized in Example 1 and Comparative Example 1 are shown in Table 1 below.

Results of Polyolefin Synthesis Using Unsupported Catalysts catalyst activation
[kg-PE / (mmol-M) (hr)] Molecular Weight
(M _w (* 10 ^-3 )) Molecular weight distribution
(M _w / M _n ) Melting point of polyolefin ( ^oC ) Example 1 Synthesis Example 2-2 2.1 1,041 3.81 131.5 Comparative Example 1 Cp ₂ ZrCl ₂ 2.0 384 2.72 134.3

Measurement results of the polyolefins synthesized in Examples 2 and 3 and Comparative Example 2 are shown in Table 2 below.

Results of Polyolefin Synthesis with Supported Catalysts Supported Catalyst activation
[g-PE / (g-cat) (hr)] Molecular Weight
(M _w (* 10 ^-3 )) Molecular Weight Distribution (M _w / M _n ) Melting Point Of Polyolefin
( ^o C) Example 2 Preparation Example 1 30 1,568 5.63 134.5 Example 3 Preparation Example 2 40 1,289 7.20 134.4 Comparative Example 2 Production Example 3 25 92 2.82 134.1

As shown in Tables 1 and 2, in Examples 1 to 3, polyolefins having a weight average molecular weight of 1 million or more were synthesized, and it was confirmed that such polyolefins had a relatively wide molecular weight distribution. And, as shown in Table 2, the supported catalyst obtained in Preparation Examples 1 and 2 has a higher activity than the supported catalyst (Preparation Example 3) used in Comparative Example 2.

In contrast, the polyolefins synthesized in Comparative Examples 1 and 2 not only had a weight average molecular weight of less than 1 million, but also had a molecular weight distribution relatively narrower than those of the polyolefins obtained in Examples 1 to 3.

Claims (13)

A transition metal catalyst compound of Formula 1; And a transition metal catalyst composition comprising a promoter:
[Chemical Formula 1]

In Chemical Formula 1,
M ¹ and M ² may be the same as or different from each other, and each is a transition metal element of Group 3 to 10,
Cp ¹ and Cp ² may be the same as or different from each other, each of which is a substituted or unsubstituted cyclopentadienyl-based functional group, and when two or more substituents are introduced into the cyclopentadienyl-based functional group, a ring may be formed as a bond between substituents ,
B ¹ is an arylene group having 5 to 40 carbon atoms or a divalent functional group represented by Chemical Formula 2,
(2)

In Chemical Formula 2,
Ary ¹ and Ary ² may be the same or different from each other, and each is an arylene-based functional group,
The B ² is an alkylene group having 1 to 20 carbon atoms, an alkylsilylene group having 1 to 20 carbon atoms, a haloalkylene group having 1 to 20 carbon atoms, and a cycloalkylene having 3 to 20 carbon atoms. (Cycloalkylene) group, an arylalkylene group having 7 to 20 carbon atoms, an arylsilylene group having 6 to 20 carbon atoms, or an alkylarylene group having 7 to 20 carbon atoms,
C is an integer of 0 to 5,
X ¹ and X ² may be the same or different from each other, and each is a phenoxy clock functional group,
Y ¹ and Y ² may be the same as or different from each other, and each of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl having 1 to 20 carbon atoms, Haloalkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, and 7 to 20 carbon atoms Alkylaryl group of 20, Arylsilyl group of 6 to 20 carbon atoms, Silylaryl group of 6 to 20 carbon atoms, Alkoxy group of 1 to 20 carbon atoms, Alkoxy of 1 to 20 carbon atoms Alkylsiloxy group, halogen (Halogen) group, amino (Amino) group or tetrahydroborate (Tetrahydroborate) group,
a and b are each an integer from the M ¹ and M ² 1 to 2 smaller than the oxidation number 5.
The method of claim 1,
The cyclopentadienyl-based functional group is a cyclopentadienyl (Cyclopentadienyl) group, Indenyl (Indenyl) or fluorenyl (Fluorenyl) transition metal catalyst composition.
The method of claim 1,
The substituent introduced into the cyclopentadienyl-based functional group is an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. (Aryl), an arylalkyl group having 7 to 20 carbon atoms (Arylalkyl), an alkylaryl group having 7 to 20 carbon atoms (Alkylaryl), an alkylsilyl group having 1 to 20 carbon atoms (Alkylsilyl), a silylalkyl group having 1 to 20 carbon atoms, Arylsilyl group having 6 to 20 carbon atoms (Arylsilyl), silylaryl group having 6 to 20 carbon atoms (Silylaryl), alkoxy group having 1 to 20 carbon atoms (alkoxy), alkylsiloxy group having 1 to 20 carbon atoms (Alkylsiloxy), 6 to 20 carbon atoms At least one transition metal catalyst composition selected from the group consisting of an aryloxy, halogen, and amino group of 20.
delete The method of claim 1,
The phenoxy functional group is a transition metal catalyst composition is a functional group of the formula
[Formula 3]

In Formula 3,
R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and each hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, and 1 carbon atom. Silylalkyl of 20 to 20, haloalkyl group of 1 to 20 carbon atoms, cycloalkyl group of 3 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms (Arylalkyl) group, C7-20 alkylaryl (Alkylaryl) group, C6-C20 arylsilyl group, C6-C20 silylaryl group, C1-C20 alkoxy Group, an alkylsiloxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a halogen group or an amino group,
R ¹ , R ² , R ³ , R ⁴ and R ⁵ Two or more of them may be joined to form a ring.
The method of claim 1,
The cocatalyst is a transition metal catalyst composition comprising at least one compound selected from the group consisting of
[Chemical Formula 4]
^{[LH] + [Z (E} ) 4] - or ^{[L] + [Z (E} ) 4] -
In Chemical Formula 4,
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,
E may be the same or different from each other, and each independently one or more selected from the group consisting of halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxy functional group and phenoxy functional group An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with a functional group,
[Formula 5]
D ( R ₉ ) ₃
In Formula 5,
D is aluminum or boron,
R ₉ may be the same as or different from each other, and each independently halogen; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with halogen; A 6 to 20 aryl group unsubstituted or substituted with halogen; An alkylaryl group having 7 to 20 carbon atoms unsubstituted or substituted with halogen, or an alkoxy group having 1 to 20 carbon atoms substituted or unsubstituted with halogen,
[Formula 6]

In Chemical Formula 6,
R ₁₀ may be the same as or different from each other, and each independently a halogen group; An alkyl group having 1 to 20 carbon atoms; Or an alkyl group having 1 to 20 carbon atoms substituted with halogen,
a is an integer of 2 or more.
The method of claim 1,
A transition metal catalyst composition fixed to a carrier.
The method of claim 7, wherein
The carrier is selected from the group consisting of silica, alumina, magnesium chloride, calcium chloride, bauxite, zeolite, magnesium oxide, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide, thorium oxide and mixtures thereof A transition metal catalyst composition comprising at least one kind.
The method of claim 1,
A transition metal catalyst composition further comprising an organic solvent.
The method of claim 1,
A transition metal catalyst composition for synthesizing a polyolefin having a weight average molecular weight of 1,000,000 or more and a molecular weight distribution (M _w / M _n ) of 3.5 or more.
A process for producing a polyolefin comprising polymerizing a olefin monomer in the presence of the transition metal catalyst composition of any one of claims 1 to 3 and 5 to 10.
The method of claim 11,
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.
The method of claim 11,
Method of producing a polyolefin to synthesize a polymer or copolymer having a weight average molecular weight of 1,000,000 or more and a molecular weight distribution (M _w / M _n ) of 3.5 or more by the polymerization reaction.