KR20100070068A - Metal complex based on new tridentate ligands and metohd for preparing olefin polymers using the same - Google Patents

Abstract

The present invention provides a novel metal compound and a method for producing an olefin polymer using the same.

Description

Metal compound containing a new tridentate ligand and a method for producing an olefin polymer using the same {METAL COMPLEX BASED ON NEW TRIDENTATE LIGANDS AND METOHD FOR PREPARING OLEFIN POLYMERS USING THE SAME}

The present invention relates to a metal compound comprising a new tridentate ligand and a method for preparing an olefin polymer using the same.

DOW announced [Me ₂ Si (Me ₄ C ₅ ) N t Bu] TiCl ₂ (Constrained-Geometry Catalyst, CGC) in the early 1990s (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, during 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 metal compounds in which various bridges and nitrogen substituents have been introduced instead of silicon bridges, and olefin polymerization using them. Opening exemplary metal compounds known to date are: (Chem. Rev. 2003, 103 , 283).

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

In addition, 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.

The compound (5) is reported by TJ Marks et al., Characterized in that the Cp derivative and the oxido ligand are 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). The compound (6) is reported by Whitby et al., Characterized by the cross-linked cyclopentadienyl ligand and oxido ligand by three carbons ( Organometallics 1999 , 18 , 348), these catalysts are syndiotactic ( syndiotactic) has been reported to be active in polystyrene polymerization. Similar compounds have also been reported by Hessen et al. ( Organometallics 1998 , 17 , 1652). The compound represented by (7) is reported by Rau et al. , And is characterized by showing activity in ethylene and ethylene / 1-hexene copolymerization at high temperature and pressure (210 ° C, 150 MPa) ( J. Organomet . Chem. 2000 , 608 , 71). In addition, the synthesis of a catalyst 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 described above, an object of the present invention is to provide a novel metal compound that can be used as a catalyst in the production of an olefin polymer, a catalyst composition comprising the same and a method for producing an olefin polymer using the same.

The present invention provides a metal compound of formula (1).

[Formula 1]

In Formula 1,

R ₁ and R ₂ are the same as or different from each other, and are each independently substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 60 carbon atoms, aryl having 6 to 60 carbon atoms, having 3 to 60 carbon atoms Consisting of heteroaryl containing O, N, S, F or P, a cyclodiene group having 5 to 60 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 60 carbon atoms and arylalkyl having 7 to 60 carbon atoms Selected from the group;

R ₃ is a single bond, alkylene having 1 to 20 carbon atoms, cycloalkylene having 5 to 60 carbon atoms, arylene having 6 to 60 carbon atoms, heteroarylene having 3 to 60 carbon atoms, cyclodienylene having 5 to 60 carbon atoms Alkenylene having 2 to 20 carbon atoms, alkylarylene having 7 to 60 carbon atoms, and arylalkylene having 7 to 60 carbon atoms;

Q ₁ is nitrogen or phosphorus and Q ₂ is oxygen or sulfur;

Q ₃ is alkylene having 1 to 20 carbon atoms, heteroalkylene having 2 to 20 carbon atoms and containing O, N, S, F or P as a hetero atom, arylene having 6 to 60 carbon atoms, alkyl arylene having 7 to 60 carbon atoms. Heteroalkyl arylene having 7 to 60 carbon atoms and containing O, N, S, F or P as a hetero atom, arylalkylene having 7 to 60 carbon atoms, O, N, S, F or P as 7 to 60 carbon atom Heteroarylalkylene containing, heteroarylene containing 3 to 60 carbon atoms, O, N, S, F or P Heteroarylene, cycloalkylene having 5 to 60 carbon atoms, O, N to 5 to 60 carbon atoms , Heterocycloalkylene containing S, F or P, cyclodienylene having 5 to 60 carbon atoms and heterocyclodienylene having 5 to 60 carbon atoms and containing O, N, S, F or P as hetero atoms Is selected from;

M is a metal of Groups 4-9 or lanthanide series metal;

X ₁ , X ₂ , X ₃ are the same as or different from each other, and are each independently a halogen radical, an alkylamido having 1 to 20 carbon atoms, an arylamido having 6 to 60 carbon atoms, an alkyl having 1 to 20 carbon atoms, and having 2 to 2 carbon atoms. Alkenyl 20, aryl having 6 to 60 carbon atoms, alkylaryl having 7 to 60 carbon atoms, arylalkyl having 7 to 60 carbon atoms, and alkylidene radicals having 1 to 20 carbon atoms.

In addition, the present invention provides a catalyst composition comprising a metal compound represented by the formula (1).

The present invention also provides a method for producing an olefin polymer using the catalyst composition.

The present invention provides a metal compound having a novel ligand, unlike conventional metal compounds having a ligand including cyclopentadiene. The present invention also provides a catalyst composition comprising the metal compound and a method for producing an olefin polymer using the same. There are no known or synthesized examples of metal compounds having new ligands, and by introducing various substituents into tridentate ligands containing heteroatoms, the electronic and steric environment around the metal can be easily controlled and ultimately generated. It is possible to control the structure and physical properties of the polyolefin.

Hereinafter, the present invention will be described in detail.

The present invention provides a metal compound of Chemical Formula 1.

In Formula 1, alkyl or alkylene has 1 to 20 carbons and is linear or branched. Alkenyl or alkenylene has 2 to 20 carbons and is straight or branched chain. Aryl or arylene has 6 to 60 carbons and can be a single ring or a condensed ring of two or more rings. Preferred examples of aryl include, but are not particularly limited to, phenyl, naphthyl, fluorenyl and the like. Heteroaryl or heteroarylene has 3 to 60 carbons and may be a single ring or a condensed ring of two or more rings. Preferred examples of heteroaryl include, but are not particularly limited to, quinolinyl, hydroquinolinyl, pyridine, pyrrole or derivatives thereof, and these may have substituents such as methyl, ethyl and phenyl. Cyclodienyl or cyclodienylene has 5 to 60 carbons and includes, but is not limited to, cyclopentadienyl and the like. Cycloalkyl or cycloalkylene has 5 to 60 carbons and includes, but is not limited to, pentane, hexane, heptane and the like. "Alkylene" and "arylene" mean divalent groups of "alkyl" and "aryl", respectively.

In Formula 1, a hetero atom or a hetero atom means S, O, P, F or N.

In Formula 1, M is a group 4 to 9 metal or lanthanide-based metal, preferably titanium (Ti), zirconium (Zr), hafnium (Hf), but is not limited thereto.

The metal compound of Formula 1 has structural features with a new tridentate ligand including nitrogen, oxygen, phosphorus or sulfur.

In Chemical Formula 1, Q ₃ is arylene having 6 to 60 carbon atoms, alkyl arylene having 7 to 60 carbon atoms, or heteroalkylaryl having 7 to 20 carbon atoms and containing O, N, S, F or P as a hetero atom. It is preferable that it is ren.

In addition, it is preferable that said Q <_1> is nitrogen.

In addition, it is preferable that said Q <_2> is oxygen.

In addition, it is preferable that R ₃ is heteroarylene containing 5 to 6 carbon atoms and containing O, N, S, F or P as hetero atoms.

In addition, Q ₁ is nitrogen, Q ₂ is oxygen, and R ₃ is a heteroarylene containing 5 to 6 carbon atoms and containing hetero atoms as O, N, S, F or P, It is more preferable for the control of the three-dimensional environment.

In addition, in Formula 1, R ₃ is most preferably heteroarylene containing 5 carbon atoms and N as a hetero atom.

In this case, the metal compound of Formula 1 can easily control the electronic and three-dimensional environment around the metal by introducing various substituents to the tridentate ligand containing a hetero atom, and ultimately the structure and physical properties of the resulting polyolefin Adjustable

Examples of the metal compound represented by Chemical Formula 1 include the following compounds, but are not limited thereto.

The metal compound according to the present invention is preferably used as a catalyst for the polymerization of the olefin monomer, but is not limited thereto. It is applicable to all fields in which the metal compound may be used.

The metal compound of Chemical Formula 1 according to the present invention may be prepared by synthesizing a tridentate ligand through a condensation reaction between a ketone compound and an amine compound and reacting it with a metal halide and an alkyl lithium. More specific examples are described in Preparation Examples below, and those skilled in the art may prepare the compound of Formula 1 with reference to the contents described in Preparation Examples.

The present invention also provides a catalyst composition comprising the metal compound of Chemical Formula 1. The catalyst composition according to the present invention may further include 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, in addition to the metal compound of Formula 1.

(3)

^{- [Al (R 5) -O} ] a -

In which R ⁵ 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 R ₅ may be the same or different from each other, and a is an integer of 2 or more. Here, "hydrocarbyl" is a monovalent group in which hydrogen atoms are removed from hydrocarbons.

[Formula 4]

J (R ⁵ ) ₃

Wherein J is aluminum or boron, R ⁵ is the same as or different from each other, and is as defined in formula (3).

[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, A is the same or different from each other, and each independently one or more hydrogen atoms is halogen, a hydrocarbyl having 1 to 20 carbon atoms, Aryl or alkyl radicals of 6 to 20 carbon atoms substituted with alkoxy or phenoxy radicals.

Among the promoter 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 activator.

The compound represented by Chemical Formula 3 is not particularly limited as long as it is an alkyl aluminoxane, but preferred examples thereof include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and particularly preferred compound is methyl aluminoxane.

The alkyl metal compound represented by Chemical Formula 4 is not particularly limited, but preferred 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, Dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like are particularly preferred. The compound is selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 5 include triethylammonium tetra (phenyl) boron, tributylammonium tetra (phenyl) boron, trimethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethyl Ammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl ) Boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethylamidiumdium tetra (phenyl) boron, N, N-diethylanilidedium tetra (phenyl) boron, N, N- Diethylanilinium tetra (pentafluorophenyl) boron, diethyl ammonium tetra (pentafluorophenyl) boron, triphenyl phosphonium tetra (phenyl) boron, trimethyl phosphonium tetra (phenyl) boron, triethyl ammonium Tetra (phenyl) aluminum, tributylammon Umtetra (phenyl) aluminum, trimethylammoniumtetra (phenyl) aluminum, tripropylammoniumtetra (phenyl) aluminum, trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (p-tolyl) aluminum, Triethylammonium 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, Tributylammonium tetra (phenyl) aluminum, trimethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, tripropylammonium tetra (p-tolyl) Boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl ) Boron, N, N-diethylanilinium tetra (pentafluorophenyl) boron, diethyl ammonium tetra (pentafluorophenyl) boron, triphenyl phosphonium tetra (phenyl) boron, triphenyl carbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (pen) Tafluorophenyl) boron, trityltetra (pentafluorophenyl) boron, and the like, but are not limited thereto.

The catalyst composition is present in an activated state by the reaction between the metal compound and the cocatalyst, which is also 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.

First contacting the metal compound of Formula 1 with the compound of Formula 3 and / or the compound of Formula 4 to obtain a mixture; And adding a compound of Chemical Formula 5 to the mixture.

Second, a method of preparing a catalyst composition may be used by contacting the metal compound of Formula 1 with the compound of Formula 3.

Third, a method of preparing a catalyst composition may be used by contacting the metal compound of Formula 1 with the compound of Formula 5.

In the first method of preparing the catalyst composition, the molar ratio of the compound of Formula 3 and the compound of Formula 4 to the metal compound of Formula 1 is preferably 1: 2 to 1: 5,000, more preferably Is 1:10 to 1: 1,000, and most preferably 1:20 to 1: 500. In addition, the molar ratio of the metal compound of Formula 1 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 amount of the compound of Formula 3 and the compound of Formula 4 is less than 2 moles relative to 1 mole of the metal compound of Formula 1, the amount of the alkylating agent is very small so that the alkylation of the metal compound does not proceed completely. In addition, when the amount of the compound of Formula 3 and the compound of Formula 4 exceeds 5,000 moles with respect to 1 mole of the metal compound of Formula 1, alkylation of the metal compound is performed, but the remaining alkylating agent and the formula 5 There is a problem that the activation of the alkylated metal compound is not completely made due to the side reaction between the activators of the. In addition, when the amount of the compound of Formula 5 with respect to 1 mole of the metal compound is less than 1 mole, the amount of the activator is relatively small, there is a problem in that the activity of the catalyst composition is not generated due to the complete activation of the metal compound, When the amount of the compound of Formula 5 is more than 25 moles relative to 1 mole of the metal compound, the metal compound is completely activated, but the excess amount of the activator does not allow the cost of the catalyst composition to be economically produced or produced. There is a problem of falling purity.

In the second method of preparing the catalyst composition, the molar ratio of the metal compound 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 amount of the compound of Formula 3 is less than 10 moles with respect to 1 mole of the metal compound, there is a problem that the activity of the catalyst composition generated due to the insufficient activation of the metal compound due to the relatively small amount of the activator is insufficient. When the amount of the compound of Formula 3 is more than 10,000 moles per 1 mole of the metal compound, the metal compound is fully activated. However, the excess amount of the activator does not allow the cost of the catalyst composition to be economically obtained or the purity of the produced polymer. Has the problem of falling.

In the third method of preparing the catalyst composition, the molar ratio of the metal compound 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.

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 metal compounds and cocatalysts of Chemical Formula 1 may be used in the form of 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 polymerization method of the present invention, the most preferable polymerization process using the catalyst composition is a solution process. When the catalyst composition is used together with an inorganic carrier such as silica, the catalyst composition can be applied to a slurry or gas phase process.

In the method for preparing a 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, toluene, benzene It can be injected by dissolving or diluting aromatic hydrocarbon solvents such as dichloromethane and hydrocarbon solvents substituted with chlorine atoms such as 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 method for producing the olefin polymer according to the present invention, the catalyst composition is not only at the reaction temperature used in the related art but also at 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 tridentate ligands containing heteroatoms, the electronic and steric environment around the metal can be easily controlled, and ultimately the structure and physical properties of the resulting polyolefin, etc. Adjustable

Hereinafter, the polymerization process of the olefin polymer is illustrated, but this is only for the purpose of illustrating the present invention, and the scope of the present invention is not intended to be 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, and hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, chlorobenzene And the like 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 introduction of at least one olefin monomer and a catalyst composition comprising the metal compound of Formula 1 and a promoter in the 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: 10000, preferably 5: 1 to 1: 100, most preferably 1: 1 to 1:20. When the molar ratio of the solvent is less than 10: 1, the amount of the solvent is too small to increase the viscosity of the fluid, which causes a problem in transferring the produced polymer. When the molar ratio of the solvent exceeds 1: 10000, 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 amount of reaction, but the temperature of the solvent is too low, the reaction temperature is also accompanied by a problem of temperature control difficult, 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 wt% in the solvent and is preferably passed to the first solvent separation process for solvent removal after a short residence time. The residence time of the resulting polymer in the reactor is 1 minute to 10 hours, preferably 3 minutes to 1 hour, most preferably 5 minutes to 30 minutes. If the residence time is less than 3 minutes, there is a problem such as productivity loss and catalyst loss due to a short residence time, and the increase in the manufacturing cost, etc., if more than 1 hour, depending on the reaction over the appropriate active period of the catalyst, The reactor is large and there is a problem of an increase in equipment costs.

c) solvent separation process

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

The pressure in the separator at this time is 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 1bar, the content of the polymer is increased, there is a problem in the transfer, if it exceeds 30bar 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.

Example

The term "overnight" means approximately 12 to 16 hours and "room temperature" refers to a temperature of 20 to 25 ° C. Synthesis of all metal compounds and preparation of experiments were carried out under a dry nitrogen atmosphere using dry box technology or using dry glass apparatus. All solvents used are HPLC grade and dried before use.

Preparation of the compound represented by formula (2)

     [Formula 2]

(Z) -3-((2- Pyridinyl ) methylamino ) -1,3- diphenylprop -2- en -One- one Manufacture of 11

Dibenzoylmethane (2.00 g, 8.92 mmol), 2- (aminomethyl) pyridine (0.643 g, 5.95 mmol), p- toluenesulfonic acid (0.051 g, 0.268 mmol) and molecular sieves (4 Å, 1.78 g) were added to toluene (50 mL). The injection was stirred at reflux for 24 hours. Thereafter, the molecular sieves were filtered through a glass filter, concentrated under reduced pressure, and separated by column chromatography to obtain a product of green oil (1.4 g, 50%).

¹ H NMR (500 MHz, CDCl ₃ ): 11.82 (br s, 1 H), 8.55-8.54 (m, 1 H), 7.92-7.90 (m, 2 H), 7.67-7.63 (m, 1 H), 7.44-7.37 ( m, 8H), 7.32-7.31 (m, 1H), 7.17-7.14 (m, 1H), 5.87 (s, 1H), 4.56 (d, J = 6.5 Hz, 2H)

[(Z) -3-((2- Pyridinyl ) methylamino ) -1,3- diphenylprop -2- en -One- one ] TiCl ₃ Manufacture of 12

Compound 11 (200 mg, 0.636 mmol) was dissolved in toluene (13 mL). TiCl ₄ (0.7 mL, 1.0 M toluene solution, 0.7 mmol) was slowly injected at −78 ° C., followed by stirring at room temperature for 24 hours. After drying under reduced pressure, the solvent was removed to give a product of reddish brown solid (317 mg, 97%).

¹ H NMR (500 MHz, CDCl ₃ ): 9.50 (d, J = 5.5 Hz, 1H), 7.92-7.89 (m, 3H), 7.57-7.25 (m, 10H), 6.43 (s, 1H), 5.14 ( s, 2H)

Claims (13)

A metal compound represented by Formula 1 below: [Formula 1]

In Formula 1, R ₁ and R ₂ are the same as or different from each other, and are each independently substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 60 carbon atoms, aryl having 6 to 60 carbon atoms, having 3 to 60 carbon atoms Consisting of heteroaryl containing O, N, S, F or P, a cyclodiene group having 5 to 60 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 60 carbon atoms and arylalkyl having 7 to 60 carbon atoms Selected from the group; R ₃ is a single bond, alkylene having 1 to 20 carbon atoms, cycloalkylene having 5 to 60 carbon atoms, arylene having 6 to 60 carbon atoms, heteroarylene having 3 to 60 carbon atoms, cyclodienylene having 5 to 60 carbon atoms Alkenylene having 2 to 20 carbon atoms, alkylarylene having 7 to 60 carbon atoms and arylalkylene having 7 to 60 carbon atoms; Q ₁ is nitrogen or phosphorus and Q ₂ is oxygen or sulfur; Q ₃ is alkylene having 1 to 20 carbon atoms, heteroalkylene having 2 to 20 carbon atoms and containing O, N, S, F or P as a hetero atom, arylene having 6 to 60 carbon atoms, alkyl arylene having 7 to 60 carbon atoms. Heteroalkyl arylene having 7 to 60 carbon atoms and containing O, N, S, F or P as a hetero atom, arylalkylene having 7 to 60 carbon atoms, O, N, S, F or P as 7 to 60 carbon atom Heteroarylalkylene containing, heteroarylene containing 3 to 60 carbon atoms, O, N, S, F or P Heteroarylene, cycloalkylene having 5 to 60 carbon atoms, O, N to 5 to 60 carbon atoms , Heterocycloalkylene containing S, F or P, cyclodienylene having 5 to 60 carbon atoms and heterocyclodienylene having 5 to 60 carbon atoms and containing O, N, S, F or P as hetero atoms Is selected from; M is a metal of Groups 4-9 or lanthanide series metal; X ₁ , X ₂ , X ₃ are the same as or different from each other, and each independently a halogen radical, an alkylamido having 1 to 20 carbon atoms, an arylamido having 6 to 60 carbon atoms, an alkyl having 1 to 20 carbon atoms, or an alkyl having 2 to 20 carbon atoms. Alkenyl, aryl having 6 to 60 carbon atoms, alkylaryl having 7 to 60 carbon atoms, arylalkyl having 7 to 60 carbon atoms and alkylidene radical having 1 to 20 carbon atoms. The method of claim 1, wherein Q ₃ is arylene having 6 to 60 carbon atoms, alkyl arylene having 7 to 60 carbon atoms, or heteroalkyl arylene having 7 to 20 carbon atoms and containing hetero atoms as O, N, S, F or P. It is a metal compound, characterized by the above-mentioned. The metal compound according to claim 1, wherein Q ₃ is phenylene, alkylphenylene or dialkylphenylene. The metal compound according to claim 1, wherein Q ₁ is nitrogen. The metal compound according to claim 1, wherein Q ₂ is oxygen. The metal compound according to claim 1, wherein R ₃ is 5 to 6 carbon atoms and heteroarylene including O, N, S, F or P as hetero atoms. The metal compound according to claim 1, wherein R ₃ is heteroarylene having 5 carbon atoms and containing N as a hetero atom. The metal compound according to claim 1, wherein the metal compound is selected from the group consisting of the following compounds.

The metal compound of any one of Claims 1-8; And At least one cocatalyst compound selected from the group consisting of a compound represented by Formula 3, a compound represented by Formula 4, and a compound represented by Formula 5 Catalyst composition comprising: (3) ^{- [Al (R 5) -O} ] a - Wherein R ⁵ 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 R ₅ May be the same as or different from each other, and a is an integer of 2 or more; [Formula 4] J (R ⁵ ) ₃ Wherein J is aluminum or boron, R ⁵ is the same as or different from each other, and is as defined in Formula 3 above; [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, A is the same or different from each other, and each independently one or more hydrogen atoms is halogen, a hydrocarbyl having 1 to 20 carbon atoms, Aryl or alkyl radicals of 6 to 20 carbon atoms substituted with alkoxy or phenoxy radicals. The catalyst composition of claim 9, wherein the metal compound and the promoter compound are in a form supported on silica or alumina. A method for preparing an olefin polymer comprising contacting a catalyst composition according to claim 9 with a monomer. The method of claim 11, wherein the monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 -At least one selected from the group consisting of dodecene, 1-tetradecene, 1-hexadecene and 1-atocene. The method of claim 11, wherein the polymer production method is performed at a polymerization temperature of 90 ° C. or more.