KR20100070674A - Group 4 transition metal complexes based on new cyclopentadienone ligand - Google Patents

Abstract

PURPOSE: A novel forth group compound is provided to introduce a substituent including a hetero atom in cyclopentadienone ligand and to control structure and physical property of olefin. CONSTITUTION: A novel forth group compound is denoted by chemical formula 1 or 2. The transition metal is used as catalyst for manufacturing olefin polymer. The catalyst composition contains a transition metal of chemical formula 1 or 2, or crude compounds of chemical formula 3(-(Al(R4)-O)a-), 4(J(R4)3), or 5([L-H]+[ZA4]- or [L]+[ZA4]-). The metal compound and crude compound is dipped in a silica or alumina.

Description

Group 4 Transition Metal Complexes Based On New Cyclopentadienone Ligand}

The present invention relates to a Group 4 transition metal compound having a novel structure, and more particularly, to a compound of the following Chemical Formula 1 containing a cyclopentadienone ligand and a method for preparing the same, and prepared using the compound. The present invention relates to a Group 4 transition metal compound of Formula 2 and a catalyst composition comprising the same.

 [Formula 1]

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring,

R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl,

Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon,

n is each independently or simultaneously an integer of 1-5.

[Formula 2]

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring,

R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl,

Each R ₃ is independently or simultaneously a halogen radical, an alkyl or aryl amido radical of 1 to 20 carbon atoms, an alkyl radical of 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical Or an alkylidene radical composed of 1 to 20 carbon atoms,

Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon,

n are each independently or simultaneously an integer of 1 to 5,

M is a Group 4 transition metal.

In the early 1990s, DOW announced [Me ₂ Si (Me ₄ C ₅ ) N t Bu] TiCl ₂ (Constrained-Geometry Catalyst, CGC) (US Pat. No. 5,064,802). The excellent aspects compared to the metallocene catalysts known up to now can be summarized into two main categories: (1) producing high molecular weight polymers with high activity even at high polymerization temperatures, and (2) 1-hexene and The copolymerizability of alpha-olefins with large steric hindrances such as 1-octene is also excellent. In addition, in the polymerization reaction, various characteristics of CGC are gradually known, and efforts to synthesize derivatives thereof and use them as polymerization catalysts have been actively conducted in academia and industry.

One approach has been to synthesize and polymerize metal compounds in which various other bridges and nitrogen substituents have been introduced instead of silicon bridges. Representative metal compounds known to date are listed below [Figure 1] ( Chem. Rev. 2003 , 103 , 283).

[Figure 1]

Compounds listed in [Figure 1] have phosphorus (1), ethylene or propylene (2), methylidene (3), and methylene (4) bridges instead of the CGC-structured silicon bridges, but ethylene polymerization or Copolymerization with alpha-olefin did not give excellent results in terms of activity and copolymerization performance compared to CGC.

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

[Figure 2]

Compound (5) was reported by TJ Marks et al. Characterized in that the Cp derivative and the oxido ligand were crosslinked by an ortho-phenylene group ( Organometallics 1997 , 16 , 5958). Compounds having the same crosslinks and polymerizations using them have also been reported by Mu et al. ( Organometallics 2004 , 23 , 540). In addition, it was reported by Rothwell et al. That an indenyl ligand and an oxido ligand were crosslinked by the same ortho-phenylene group ( Chem. Commun. 2003 , 1034). Compound (6), reported by Whitby et al., Is characterized by the crosslinking of cyclopentanienyl ligands and oxido ligands by three carbons ( Organometallics 1999 , 18 , 348). It was reported to be active. Similar compounds have also been reported by Hessen et al. ( Organometallics 1998 , 17 , 1652). Compound shown in Compound (7) is reported by Rau et al. Is characterized by showing activity in the copolymerization of ethylene and ethylene / 1-hexene at high temperature and pressure (210 ° C., 150 MPa) ( J. Organomet. Chem. 2000 , 608 , 71). In addition, a catalyst synthesis compound 8 having a similar structure and high temperature and high pressure polymerization using the same have been patented by Sumitomo (US Pat. No. 6,548,686).

Recently, a compound such as compound (9) having a pyridyl-amide ligand deviating from the CGC structure has been reported by DOW (US 2004/0220050, J. Am. Chem. Soc . 2007 , 129 , 7831). The catalyst is capable of high temperature polymerization and has multiple active sites, thus showing activity against ethylene / octene copolymers having a broad molecular weight distribution.

Of all these attempts, however, only a few catalysts are actually used in commercial plants.

In order to solve the problems of the prior art as described above, the first technical problem to be achieved by the present invention is to provide a novel compound containing a cyclopentadienone ligand to which a silyl group is introduced and a method for preparing the same.

It is a second object of the present invention to provide a Group 4 transition metal compound having a novel structure prepared using the compound, and a catalyst composition including the compound, and to provide an olefin polymer prepared using the catalyst composition. will be.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a compound of a novel structure including a cyclopentadienone ligand to which a silyl group prepared by the following scheme is introduced.

[Scheme]

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring,

R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl,

Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon,

n is each independently or simultaneously an integer of 1-5.

In addition, using the compound of Formula 1 provides a metal compound represented by the following [Formula 2].

[Formula 2]

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring,

R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl,

Each R ₃ is independently or simultaneously a halogen radical, an alkyl or aryl amido radical having 1 to 20 carbon atoms, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical or carbon atoms Selected from alkylidene radicals of 1 to 20,

Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon,

n are each independently or simultaneously an integer of 1 to 5,

M is a Group 4 transition metal.

As described above, according to the present invention, a compound having a novel structure having a cyclopentadienone ligand to which a silyl group is introduced is provided, and a novel Group 4 transition metal compound prepared using the same, and a method of preparing the same do. In addition, the present invention provides a catalyst composition comprising the metal compound and an olefin polymer prepared using the same. The metal compound having the new ligand has no known or synthesized examples, and by introducing a substituent containing a hetero atom such as a silyl group in the cyclopentadienone ligand, the electronic and steric environment around the metal can be easily controlled. And ultimately control of the structure and physical properties of the resulting olefin polymer.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention provides a compound having a novel structure having a cyclopentadienone ligand in which a silyl group is introduced by a synthesis method represented by the following scheme.

[Scheme]

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring,

R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl,

Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon,

n is each independently or simultaneously an integer of 1-5.

In addition, the present invention obtains a compound represented by the following [Formula 2] using the compound of [Formula 1] prepared by the above reaction scheme in order to achieve the second technical problem.

[Formula 2]

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring,

R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl,

Each R ₃ is independently or simultaneously a halogen radical, an alkyl or aryl amido radical having 1 to 20 carbon atoms, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical or carbon atoms Selected from alkylidene radicals of 1 to 20,

Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon,

n are each independently or simultaneously an integer of 1 to 5,

M is a Group 4 transition metal.

To obtain a compound represented by the following [Formula 2] using the compound of [Formula 1] may be used a synthetic method represented by the following reaction formula, but is not limited thereto.

[Scheme]

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring,

R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl,

Each R ₃ is independently or simultaneously a halogen radical, an alkyl or aryl amido radical having 1 to 20 carbon atoms, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical or carbon atoms Selected from alkylidene radicals of 1 to 20,

Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon,

n are each independently or simultaneously an integer of 1 to 5,

M is a Group 4 transition metal.

That is, the formation of non-on [Formula 2] Production of metal compounds, while the addition of Q ₁ and Q ₂ including the R ₁ to alkynyl containing the Q ₃ and introducing a carbonyl group, the cyclo-penta die in accordance with the present invention (the Compound of Formula 1), and then reacting the same with a metal halide and alkyl lithium. More specific examples are described in Preparation Examples below, and those skilled in the art may prepare the compound of Formula 2 with reference to the contents described in Preparation Examples.

In this case, the metal compound of [Formula 2] can easily control the electronic and three-dimensional environment around the metal by introducing a substituent containing a hetero atom such as a silyl group in the cyclopentadienone ligand and ultimately produced The structure and physical properties of the olefin polymer can be controlled.

The compound of [Formula 2] according to the present invention is preferably used to prepare a catalyst for the polymerization of the olefin monomer, but is not limited thereto, and other applicable to all fields in which the transition metal compound may be used.

In the present invention, as a more preferred compound for controlling the electronic and three-dimensional environment around the metal, in Formula 2, Q ₁ and Q ₂ are silicon, Q ₃ is carbon, and n is preferably 1.

The present invention also provides a catalyst composition comprising the metal compound of the above [Formula 2]. The catalyst composition according to the present invention comprises at least one cocatalyst compound selected from the group consisting of the compound of the following Chemical Formula 3, the compound of the following Chemical Formula 4, and the compound of the following Chemical Formula 5, in addition to the metal compound of [Formula 2] It may further include.

(3)

_{- [Al (R 4) -O} ] a -

Wherein R ₄ is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, each of R ₄ is the same as or different from each other, and a is an integer of 2 or more . In the above description, hydrocarbyl is a monovalent group in which hydrogen atoms are removed from hydrocarbons.

[Formula 4]

J (R ₄ ) ₃

Wherein J is aluminum or boron, R ₄ is a halogen radical, a hydrocarbyl radical of 1 to 20 carbon atoms, or a hydrocarbyl radical of 1 to 20 carbon atoms substituted with halogen, and each R ₄ is the same or different , A halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen.

[Chemical Formula 5]

_{^{[LH] + [ZA 4]}} - or _{^{[L] + [ZA 4]}} -

Wherein L is a neutral or cationic Lewis acid, H is a hydrogen atom, Z is a Group 13 element, and A is each independently at least one hydrogen atom is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy radicals Aryl or alkyl radical having 6 to 20 carbon atoms substituted with.

Among the cocatalyst compounds, the compound of [Formula 3] and the compound of [Formula 4] may alternatively be represented by an alkylating agent, and the compound of [Formula 5] may be represented by an activating agent.

The compound represented by [Formula 3] is not particularly limited as long as it is alkyl aluminoxane, but specific examples thereof include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and preferably methyl aluminoxane. have.

The alkyl metal compound represented by [Formula 4] is not particularly limited, but specific examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum and 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 Seed, dimethylaluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, preferably trimethyl aluminum, triethyl aluminum, triisobutyl aluminum and the like can be used. have.

Examples of the compound represented by the above [Formula 5] include triethyl ammonium tetra (phenyl) boron, tributyl ammonium tetra (phenyl) boron, trimethyl ammonium tetra (phenyl) boron, tripropyl ammonium tetra (phenyl) boron , Trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoro Romethylphenyl) boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethylamidium 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, tributylarm 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 ( Pentafluorophenyl) aluminum, N, N-diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (pentafluoro Rophenyl) aluminum, diethylammonium tetra (pentafluorophenyl) aluminum, triphenylphosphonium tetra (phenyl) aluminum, trimethylphosphonium tetra (phenyl) aluminum, triethylammonium tetra (phenyl) aluminum , Tributyl ammonium tetra (phenyl) aluminum, trimethyl ammonium tetra (phenyl) boron, tripropyl ammonium tetra (phenyl) boron, trimethyl ammonium tetra (p-tolyl) boron, tripropyl ammonium 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 And the like as other fluorophenyl) boron, trityl tetra (pentafluorophenyl) boron.

The catalyst composition is present in an activated state by the reaction between the transition metal compound and the promoter and is sometimes referred to as an activated catalyst composition. However, since it is known in the art that the catalyst composition exists in an activated state, the term activated catalyst composition is not used separately herein. The catalyst composition can be used for olefin homopolymerization or copolymerization.

As a method for producing the catalyst composition according to the present invention, for example, the following method can be used.

Firstly contacting the metal compound of [Formula 2] with the compound of [Formula 3] and / or the compound of [Formula 4] to obtain a mixture; And adding the compound of [Formula 5] to the mixture.

Secondly, a method of preparing a catalyst composition by contacting the metal compound of [Formula 2] and the compound of [Formula 3] may be used.

Third, a method of preparing a catalyst composition may be used by contacting the metal compound of [Formula 2] and the compound of [Formula 5].

In the case of the first method of preparing the catalyst composition, the molar ratio of the compound of [Formula 3] and / or the compound of Formula [4] is 1: 2 to 1: 5,000 is preferred, more preferably 1:10 to 1: 1,000, most preferably 1:20 to 1: 500. If the molar ratio is less than 1: 2, the amount of alkylating agent is so small that the alkylation of the metal compound does not proceed completely. If the molar ratio exceeds 1: 5,000, the alkylation of the metal compound is achieved, but the excess Due to the side reaction between the alkylating agent and the activator of [Formula 5] there is a problem that the activation of the alkylated metal compound is not fully made.

In addition, the molar ratio of the metal compound of [Formula 2] to the compound of [Formula 5] is preferably 1: 1 to 1:25, more preferably 1: 1 to 1:10, and most preferably 1 : 2 to 1: 5. When the molar ratio is less than 1: 1, the amount of the activator is relatively small, and thus the activity of the catalyst composition generated due to the incomplete activation of the metal compound is inferior. When the molar ratio exceeds 1:25, the metal Although the activation of the compound is completely made, there is a problem in that the unit cost of the catalyst composition is not economically reduced or the purity of the resulting polymer is reduced due to the excess activator remaining.

In the second method of preparing the catalyst composition, the molar ratio of the metal compound of Formula 2 to the compound of Formula 3 is preferably 1:10 to 1: 10,000, more preferably 1: 100 to 1: 5,000, most preferably 1: 500 to 1: 2,000. When the molar ratio is less than 1:10, the amount of the activator is relatively small, and thus the activity of the catalyst composition generated due to the incomplete activation of the metal compound is inferior, and when the molar ratio exceeds 1: 10,000, the metal Although the activation of the compound is completely made, there is a problem in that the unit cost of the catalyst composition is not economically reduced or the purity of the resulting polymer is reduced due to the excess activator remaining.

In the third method of preparing the catalyst composition, the molar ratio of the metal compound of Formula 2 to the compound of Formula 5 is preferably 1: 1 to 1:25, more preferably 1: 1 to 1:10, most preferably 1: 2 to 1: 5. When the molar ratio is less than 1: 1, the amount of the activator is relatively small, and thus the activity of the catalyst composition generated due to the incomplete activation of the metal compound is inferior. When the molar ratio exceeds 1:25, the metal Although the activation of the compound is completely made, there is a problem in that the unit cost of the catalyst composition is not economically reduced or the purity of the resulting polymer is reduced due to the excess activator remaining.

Hydrocarbon solvents such as pentane, hexane, heptane and the like or aromatic solvents such as benzene and toluene may be used as the reaction solvent in the preparation of the catalyst composition, but the solvent is not necessarily limited thereto and any solvents available in the art may be used. Can be.

In addition, the transition metal compounds and cocatalysts of the above [Formula 2] may be used in a form supported on silica or alumina.

The present invention also provides a method for producing an olefin polymer using the catalyst composition. The process according to the invention can be carried out by contacting said catalyst composition with a monomer. According to the method for producing the olefin polymer of the present invention, an olefin homopolymer or an olefin copolymer can be provided.

In the method for preparing an olefin polymer according to the present invention, the catalyst composition is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and toluene, Aqueous solvents may be dissolved or diluted in aromatic hydrocarbon solvents such as benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, and chlorobenzene. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.

Examples of the olefin monomer that can be polymerized using the metal compounds and the cocatalyst include ethylene, alpha-olefin, cyclic olefin, and the like, and diene olefin monomer or triene olefin monomer having two or more double bonds. Polymerization is possible. Specific examples of the monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethyl styrene, etc., These monomers may be mixed and copolymerized. When the olefin polymer is a copolymer of ethylene and other comonomers, the monomers constituting the copolymer are in the group consisting of propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene It is preferred that it is at least one comonomer selected.

In particular, in the process for producing the olefin polymer according to the present invention, the catalyst composition is not only at the reaction temperature conventionally used, but also at a high reaction temperature of 90 ° C. or higher, even at 140 ° C. or higher, such as ethylene and 1-octene. Copolymerization of monomers with high steric hindrance is also possible, and by introducing various substituents into substituents having heteroatoms such as amine groups and imine groups, it is possible to easily control the electronic and steric environment around the metal and ultimately produce olefin polymers. It is possible to adjust the structure and physical properties.

The most preferred polymerization process using the catalyst composition in the polymerization process of the present invention is a solution process, and when the composition is used together with an inorganic carrier such as silica, it is also applicable to a slurry or gas phase process.

Hereinafter, the polymerization process of the olefin polymer is exemplified, but this is only for the purpose of illustrating the present invention, and the scope of the present invention is not limited by the following contents.

The reactor used in the process for producing the polymer according to the invention is preferably a continuous stirred reactor (CSTR) or a continuous flow reactor (PFR). The reactor is preferably arranged in two or more in series or in parallel. In addition, the preparation method preferably further comprises a separator for continuously separating the solvent and unreacted monomer from the reaction mixture.

When the method of preparing a polymer according to the present invention is performed 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, and more specifically, as follows.

a) catalytic process

The catalyst composition according to the present invention may be injected by dissolving or diluting an aliphatic or aromatic solvent having 5 to 12 carbon atoms or unsubstituted with a halogen suitable for an olefin polymerization process. For example, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane, and isomers thereof, aromatic hydrocarbon solvents such as toluene, xylene, benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, chlorobenzene, etc. This can be used. The solvent used here is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating with a small amount of alkylaluminum or the like, and can also be carried out using an excessive amount of a promoter.

b) polymerization process

The polymerization process is carried out by introducing a catalyst composition comprising the metal compound and the cocatalyst of the above [Formula 2] and at least one olefin monomer in a reactor. In the case of solution phase and slurry phase polymerization, a solvent is injected onto the reactor. In the case of solution polymerization, a mixture of a solvent, a catalyst composition and a monomer is present in the reactor.

The molar ratio of monomer to solvent suitable for the 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 monomer to solvent is 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 is a problem in the transfer of the produced polymer, and when the molar ratio of the solvent exceeds 1: 10,000, Since the amount is more than necessary, there is a problem such as an increase in equipment and an increase in energy cost due to the purification of the solvent.

The solvent is preferably introduced into the reactor at a temperature of −40 ° C. to 150 ° C. using a heater or a freezer, whereby the polymerization is started together with the monomer and the catalyst composition. 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 a drop in temperature control is difficult problem, if the temperature exceeds 150 ℃ The temperature of the solvent is too high, there is a problem that the heat removal of the reaction heat due to the reaction is difficult.

A high capacity pump raises the pressure above 50 bar to supply the feeds (solvent, monomer, catalyst composition, etc.), thereby passing the mixture of the feeds without additional pumping between the reactor arrangement, pressure dropping device and separator. You can.

The internal temperature of the reactor suitable for the present invention, ie the polymerization reaction temperature, is -15 ° C to 300 ° C, preferably 50 ° C to 200 ° C, most preferably 100 ° C to 200 ° C. 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.

The internal pressure of the reactor suitable in the present invention is 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, and when it exceeds 300 bar, there is a problem of an increase in equipment cost, such as an apparatus cost according to a high pressure.

The polymer produced in the reactor is maintained at a concentration of less than 20% by weight 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 is suitably 1 to 30 bar, preferably 1 to 10 bar, most preferably 3 to 8 bar. The temperature in the separator is suitably 150 ° C to 250 ° C, preferably 170 ° C to 230 ° C, most preferably 180 ° C to 230 ° C.

If the pressure in the separator is less than 1 bar, the content of the polymer is increased, there is a problem in the transfer, if it exceeds 30 bar there is a problem that the separation of the solvent used in the polymerization process is difficult. 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, and when the temperature is less than 250 ° C., there is a problem of discoloration 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. Solvents 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.

Hereinafter, the present invention will be described in more detail based on the following examples. These examples are provided to aid the understanding of the present invention, and the scope of the present invention is not limited thereto.

EXAMPLE

The synthesis of all metal complexes and the preparation of experiments are carried out in a dry nitrogen atmosphere using dry box technology or using dry glass apparatus. All solvents used are HPLC grade and dried before use.

<Examples 1 to 3> Preparation process of the compound represented by [Formula 2] according to the present invention

Example 1

Preparation of 1,7-bis (triphenylsilyl) hepta-1,6-dyne (1,7-Bis (triphenylsilyl) hepta-1,6-diyne)

Inject 500 mg (5.4 mmol) of 1,6-heptadine (1,6-Heptadiyne) into 20 mL of THF and stir. Then, 13.5 mmol (5.4 mL, 2.5 M hexane aqueous solution) of n-BuLi at −78 ° C. were slowly introduced into the solution, followed by stirring at 0 ° C. for 3 hours. After observing the color of the solution turning from yellow to white, 3.98 g (13.5 mmol) of triphenylsilyl chloride are injected at 0 ° C. and stirred at room temperature for 24 hours.

After the reaction, quench by adding 1N hydrochloric acid (HCl) aqueous solution, extract with methylene chloride (CH ₂ Cl ₂ ), remove water with sodium sulfate (Na ₂ SO ₄ ), and then remove the glass filter. Filter with.

The filtrate was concentrated under reduced pressure and recrystallized from hexane to give the product as a white solid (3.05 g, 93%).

¹ H NMR (500 MHz, CDCl ₃ ): 7.66-7.62 (m, 12H), 7.41-7.32 (m, 18H), 2.61-2.56 (t, 4H), 1.94 (m, 2H)

Example 2 Preparation of Compound Represented by Formula 1 According to the Present Invention

4,5-dihydro-1,3-bis (triphenylsilyl) pentane-2 (4H) -one (4,5-dihydro-1,3-bis (triphenylsilyl) pentalen-2 (4H) -one) Manufacture

A solution of 913 mg (1.5 mmol) of the compound prepared in Example 1 in 150 mL of toluene is slowly injected into a solution prepared by dissolving 342 mg (1.0 mmol) of dicobalt octacarbonyl in 130 mL of toluene. It is stirred at 120 ° C. for 1 hour and then cooled to form a solid precipitate.

The precipitate is filtered through a glass filter filled with silica gel and the filtrate is concentrated. The concentrated mixture is separated by column chromatography to give the product as a yellow solid (911 mg, 95%).

¹ H NMR (500 MHz, CDCl ₃ ): 7.55-7.52 (m, 12H), 7.42-7.31 (m, 18H), 1.88 (t, 4H), 1.69 (m, 2H)

Example 3 Preparation of Transition Metal Compounds Represented by Formula 2 According to the Present Invention

[4,5-dihydro-1,3-bis (triphenylsilyl) pentane-2 (4H) -one] titanium chloride ([4,5-dihydro-1,3-bis (triphenylsilyl) pentalen-2 ( 4H) -one] TiCl ₃ Manufacturing

911 mg (1.43 mmol) of the compound prepared in Example 2 was dissolved in 80 mL of THF, and 1.43 mmol (1.43 mL, 1.0 M of toluene aqueous solution) of titanium chloride (TiCl ₄ ) was slowly added thereto at 20 to 25 ° C. The mixture is stirred at 80 ° C. for about 12 to 16 hours.

After the solvent is removed here, hexane is injected to precipitate a solid product. The solid product was filtered through a glass filter under argon, washed several times with hexane, and dried under reduced pressure to obtain a yellow solid (849 mg, 75%).

The structure of the compound prepared in Example 3 is as follows.

¹ H NMR (500 MHz, CDCl ₃ ): 7.75-7.65 (m, 12H), 7.43-7.32 (m, 18H), 2.13-2.05 (m, 2H), 1.85-1.81 (m, 1H), 1.30-1.16 (m, 3 H)

Example 4 Ethylene Polymerization

100 mL of toluene solvent was added to a 500 mL Andrews Glass reactor, and the reactor was preheated to 90 ° C. 2 umol of the catalyst prepared in Example 3 and 25 umol of trityl tetrakis (pentafluorophenyl) borate cocatalyst were filled in sequence using a syringe. At this time, an ethylene pressure of 3 bar was added and the polymerization reaction was carried out for 10 minutes, then the remaining ethylene was removed, and the polymer solution was precipitated by adding an excess of methanol. The obtained polymer is dried in a 60 ° C. vacuum oven for at least 24 hours. The polymerization conditions of Example 4 are shown in Table 1 below.

Example 5 Ethylene Polymerization

A polymer was prepared in the same manner as in Example 1, except that 5 umol of the catalyst prepared in Example 3 was used. The polymerization conditions of Example 5 are shown in Table 1 below.

Example 6 Ethylene, 1-Octene Copolymerization

100 mL of toluene and 4.05 mL of 1-octene are added to a 500 mL Andrews Glass reactor, and the reactor is preheated to 90 ° C. Using a syringe, 5 umol of the catalyst prepared in Example 3 and 25 umol of trityl tetrakis (pentafluorophenyl) borate cocatalyst were sequentially filled. At this time, an ethylene pressure of 3 bar was added, the copolymerization reaction was carried out for 10 minutes, the remaining ethylene was removed, and the polymer solution was precipitated by adding excess methanol. The obtained polymer is dried in a 60 ° C. vacuum oven for at least 24 hours. The polymerization conditions of Example 6 are shown in Table 1 below.

Comparative Example 1 Ethylene Polymerization

100 mL of toluene solvent was added to a 500 mL Andrews Glass reactor, and the reactor was preheated to 90 ° C. Using a syringe, 5 umol of the following CGC catalyst and 25 umol of trityl tetrakis (pentafluorophenyl) borate cocatalyst are filled in sequence. At this time, an ethylene pressure of 3 bar was added, the copolymerization reaction was carried out for 10 minutes, the remaining ethylene was removed, and the polymer solution was precipitated by adding excess methanol. The obtained polymer is dried in a 60 ° C. vacuum oven for at least 24 hours. The polymerization conditions of Comparative Example 1 are shown in Table 1 below.

Comparative Example 2 Ethylene, 1-octene copolymerization

100 mL of toluene and 4.05 mL of 1-octene are added to a 500 mL Andrews Glass reactor, and the reactor is preheated to 90 ° C. Using a syringe, 5 umol of the CGC catalyst and 25 umol of the trityl tetrakis (pentafluorophenyl) borate promoter are sequentially filled as in Comparative Example 1. At this time, an ethylene pressure of 3 bar was added, the copolymerization reaction was carried out for 10 minutes, the remaining ethylene was removed, and the polymer solution was precipitated by adding excess methanol. The obtained polymer is dried in a 60 ° C. vacuum oven for at least 24 hours. The polymerization conditions of Comparative Example 2 are shown in Table 1 below.

Temperature
(℃) Ethylene
(bar) Catalyst type Catalytic amount
(umol) Promoter amount
(umol) Comonomer
(ml) Example 4 90 3 Example 3 2 25 - Example 5 90 3 Example 3 5 25 - Example 6 90 3 Example 3 5 25 4.05 Comparative Example 1 90 3 CGC 5 25 - Comparative Example 2 90 3 CGC 5 25 4.05

Test Example

The polymers prepared in Examples 4 to 6 and Comparative Examples 1 and 2 were evaluated by the following methods, and the results are shown in the following [Table 2].

The organic reagents and solvents used in the examples and comparative examples were purchased from Aldrich and Merck and purified by standard methods. The following molecular weight distribution (PDI) was calculated by measuring the number average molecular weight (Mn) and the weight average molecular weight (Mw) using gel permeation chromatography (GPC) and dividing the weight average molecular weight by the number average molecular weight.

The melting point (Tm) of the obtained polymer was obtained by using DSC (Differential Scanning Calorimeter) 2920 manufactured by TA. That is, the temperature was increased to 200 ° C., then maintained at that temperature for 5 minutes and then lowered to 30 ° C. and the temperature increased again to make the top of the DSC curve the melting point. At this time, the rate of temperature rise and fall is 10 ° C./min, and a melting point is obtained while the second temperature is rising.

In addition, the density of the polymer was measured in a sample treated with an antioxidant (1,000 ppm) using a 180 ° C. press mold to make a sheet having a thickness of 3 mm and a radius of 2 cm, and then cooled to 10 ° C./min. (Mettler) was measured on a balance.

Yield (g) Density (g / cm ³ ) Tm (℃) Mw PDI Example 4 9.12 0.923 124.7 100,258 2.1 Example 5 10.36 0.919 123.9 103,697 2.3 Example 6 12.92 0.887 82.4 133,524 3.1 Comparative Example 1 7.52 0.926 128.7 96,054 2.0 Comparative Example 2 10.58 0.911 91.5 129,920 2.2

As shown in Table 2, it can be seen that the catalyst composition comprising the transition metal compound according to the present invention exhibits catalytic activity when polymerizing the olefin polymer (Examples 4 to 6).

Although the present invention has been described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the present invention, and such modifications and modifications fall within the scope of the appended claims. It is also natural.

Claims (18)

The compound represented by following [Formula 1]. [Formula 1]

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring, R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl, Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon, n is each independently or simultaneously an integer of 1-5. The method of claim 1, In Formula 1, Q ₁ and Q ₂ are silicon, Q ₃ is carbon, n is 1, characterized in that the compound. The manufacturing method of the compound by the synthesis method shown by following Reaction [scheme 1]. Scheme 1

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring, R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl, Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon, n is each independently or simultaneously an integer of 1-5. The method of claim 3, wherein Compound of Formula 1 is a method for producing a compound, characterized in that prepared by the synthesis method represented by the following [Scheme 2]. Scheme 2

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring, R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl, Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon, n is each independently or simultaneously an integer of 1-5. The method according to claim 3 or 4, Said Q <_1> and Q <_2> are silicon, Q <_3> is carbon, n is 1, The manufacturing method of the compound characterized by the above-mentioned. A metal compound represented by the following [Formula 2]. [Formula 2]

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring, R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl, Each R ₃ is independently or simultaneously a halogen radical, an alkyl or aryl amido radical having 1 to 20 carbon atoms, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical or carbon atoms Selected from alkylidene radicals of 1 to 20, Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon, n are each independently or simultaneously an integer of 1 to 5, M is a Group 4 transition metal. The method of claim 6, In Chemical Formula 2, Q ₁ and Q ₂ are silicon, Q ₃ is carbon, and n is 1, wherein the metal compound. The method of claim 6, The compound is a metal compound, characterized in that used as a catalyst for producing an olefin polymer. The manufacturing method of a compound by the synthesis method shown by following Reaction [scheme 3]. Scheme 3

Wherein R ₁ is each independently or simultaneously hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, arylalkyl, or an alkyl or aryl radical containing 1 to 20 carbon atoms Connected to each other by alkylidine radicals to form a ring, R ₂ is hydrogen, alkyl or aryl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl, or arylalkyl, Each R ₃ is independently or simultaneously a halogen radical, alkyl or aryl amido radical of 1 to 20 carbon atoms, alkyl radical of 1 to 20 carbon atoms, alkenyl radical, aryl radical, alkylaryl radical, arylalkyl radical or carbon Selected from alkylidene radicals of 1 to 20, Q ₁ , Q ₂ , Q ₃ are each independently or simultaneously carbon, nitrogen, oxygen, sulfur, phosphorus, or silicon, n are each independently or simultaneously an integer of 1 to 5, M is a Group 4 transition metal. The method of claim 9, Said Q <_1> and Q <_2> are silicon, Q <_3> is carbon, n is 1, The manufacturing method of the compound characterized by the above-mentioned. A metal compound according to any one of claims 6 to 8; And At least one cocatalyst compound selected from the group consisting of a compound of Formula 3, a compound of Formula 4, and a compound of Formula 5; Catalyst composition comprising a. (3) _{- [Al (R 4) -O} ] a - Wherein R ₄ is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, each of R ₄ is the same as or different from each other, and a is an integer of 2 or more . [Formula 4] J (R ₄ ) ₃ Wherein J is aluminum or boron, R ₄ is a halogen radical, a hydrocarbyl radical of 1 to 20 carbon atoms, or a hydrocarbyl radical of 1 to 20 carbon atoms substituted with halogen, and each R ₄ is the same or different , A halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen. [Chemical Formula 5] _{^{[LH] + [ZA 4]}} - or _{^{[L] + [ZA 4]}} - Wherein L is a neutral or cationic Lewis acid, H is a hydrogen atom, Z is a Group 13 element, and A is each independently at least one hydrogen atom is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy radicals Aryl or alkyl radical having 6 to 20 carbon atoms substituted with. The method of claim 11, Catalyst composition, characterized in that the molar ratio of the metal compound to the compound of [Formula 3] or [Formula 4] is 1: 2 to 1: 5,000. The method of claim 11, Catalyst composition, characterized in that the molar ratio of the metal compound to the compound of [Formula 5] is 1: 1 to 1:25. The method of claim 11, The metal compound and the cocatalyst compound are in a form supported on silica or alumina. The method of claim 11, The catalyst composition is a catalyst composition, characterized in that used as a catalyst for producing an olefin polymer. An olefin polymer, which is prepared using a catalyst composition according to any one of claims 11 to 15 when polymerizing an olefinic monomer. The method of claim 16, The olefinic monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene Olefin polymer, characterized in that at least one member selected from the group consisting of 1, tetradecene, 1-hexadecene and 1- itocene. The method of claim 16, The olefin polymer is characterized in that the prepared at a polymerization temperature of 90 ℃ or more.