KR100853433B1 - Catalyst composition comprising transition metal compound and process for polymerization of olefins by the same - Google Patents

Abstract

The present invention relates to a catalyst composition comprising a transition metal compound and an olefin polymerization method using the same, in particular a catalyst composition comprising a transition metal compound known as a metallocene catalyst, specifically a monocyclopentani having an amido group introduced therein. Olefin polymerization using a novel transition metal compound coordinated with a dienyl ligand.

The transition metal compound according to the present invention has a phenylene bridge, unlike conventional transition metal compounds having a silicon bridge and an oxido ligand, and thus the monomer structure is more easily accessible, and the robust five-membered ring structure can be stably maintained. In the continuous solution polymerization process using the catalyst composition containing the transition metal compound, it is possible to prepare a variety of copolymers at a wide range of temperatures and pressures. It is possible to produce ultra low density polyolefin copolymers of less than g / cc.

Description

Catalyst composition comprising a transition metal compound and a method for producing an olefin polymer using the same {Catalyst composition comprising transition metal compound and process for polymerization of olefins by the same}

The present invention relates to a catalyst composition comprising a transition metal compound and an olefin polymerization method using the same, in particular a catalyst composition comprising a transition metal compound known as a metallocene catalyst, specifically a monocyclopentani having an amido group introduced therein. Olefin polymerization using a novel transition metal compound coordinated with a dienyl ligand.

Dow published [Me ₂ Si (Me ₄ C ₅ ) N t Bu] TiCl ₂ (Constrained-Geometry Catalyst, hereinafter abbreviated as CGC) in the early 1990s (see US Patent No. 5,064,802), In the copolymerization reaction between ethylene and alpha-olefin, the CGC is superior to the metallocene catalysts known to the prior art in two main ways: (1) high molecular weight with high activity even at high polymerization temperature It produces a polymer of (2) and (2) the copolymerizability of alpha-olefins with high steric hindrance such as 1-hexene and 1-octene is also excellent. In addition, during the polymerization reaction, various characteristics of CGC are gradually known, and efforts have been actively made to synthesize derivatives thereof and use them as polymerization catalysts.

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 as in Chemical Formulas 21 to 24 ( Chem. Rev. 2003, 103 , 283).

The compounds of Formulas 21 to 24 have phosphorus (Chemical Formula 21), ethylene or propylene (Chemical Formula 22), methylidene (Chemical Formula 23), and methylene (Chemical Formula 24) bridges instead of the CGC-structured silicon bridges, respectively. No improved results have been obtained in terms of activity or copolymerization performance compared to CGC in ethylene polymerization or copolymerization with alpha-olefins.

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

Compound 25 is characterized by the cross-linked Cp (cyclopentadiene) derivative and oxido ligand by an ortho-phenylene group as reported by TJ Marks et al. ( Organometallics 1997, 16 , 5958). Compounds with 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 (see Chem. Commun. 2003, 1034). The compound of Formula 26 is reported by Whitby et al. Characterized in that the cyclopentanienyl ligand and the oxido ligand are pierched by three carbons (see Organometallics 1999, 18 , 348). It has been reported to be active in syndiotactic polystyrene polymerization. Similar compounds have also been reported by Hessen et al. ( Organometallics 1998, 17 , 1652). The compound of Formula 27, reported by Rau et al. , Is characterized by its activity in ethylene polymerization and ethylene / 1-hexene copolymerization at high temperature and pressure (210 ° C., 150 MPa) (see J. Organomet. Chem. 2000, 608). , 71). In addition, a catalyst synthesis having a similar structure (formula 28) and high temperature and high pressure polymerization using the same have been disclosed by Sumitomo (see US Patent No. 6,548,686).

However, among the above attempts, few catalysts are actually applied in commercial plants, and there is still a need for development of catalysts showing improved polymerization performance and continuous solution polymerization processes suitable therefor.

The technical problem to be achieved by the present invention is to provide a novel transition metal compound having a phenylene bridge coordinated with a monocyclopentanidienyl ligand to which amido groups are introduced, and a catalyst composition comprising the same.

Another technical problem to be achieved by the present invention is to provide a method for producing an olefin polymer using the catalyst composition.

The present invention to achieve the above technical problem,

It provides a transition metal compound of formula (1);

Where

R ₁ and R ₂ are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; Aryl groups having 6 to 30 carbon atoms; Silyl groups having 0 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Alkylaryl groups having 7 to 30 carbon atoms; Arylalkyl groups having 7 to 30 carbon atoms; A metalloid radical of a Group 14 metal substituted with a hydrocarbon group; R ₁ and R ₂ may be linked to each other by an alkylidene group having 2 to 30 carbon atoms substituted with an alkyl group and an aryl group to form a ring;

Each R ₄ is independently a hydrogen atom; Halogen atom; An alkyl group having 1 to 20 carbon atoms; Carbon atoms, represents a group of aryl of 6 to 30, wherein R ₄ of the two R ₄ may be a folded ring (fused ring) structure are connected to each other, and;

R ₃ is an alkylsulfonyl group having 1 to 20 carbon atoms; Arylsulfonyl group having 6 to 30 carbon atoms; Silylsulfonyl groups having 0 to 20 carbon atoms; An alkylcarbonyl group having 1 to 20 carbon atoms; Arylcarbonyl group having 7 to 30 carbon atoms; Silylcarbonyl groups having 1 to 20 carbon atoms; Alkyl carboxyl groups having 2 to 20 carbon atoms; Aryl carboxy groups having 7 to 30 carbon atoms; Alkyl phosphonyl groups having 1 to 20 carbon atoms; An arylphosphonyl group having 6 to 30 carbon atoms;

M represents a Group 4 transition metal;

Q ₁ and Q ₂ are each independently a halogen atom; An alkyl group having 1 to 20 carbon atoms; Arylamido groups having 6 to 30 carbon atoms; An alkyl group having 1 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Aryl groups having 6 to 30 carbon atoms; Alkylaryl groups having 7 to 30 carbon atoms; Arylalkyl groups having 7 to 30 carbon atoms; Or an alkylidene group having 1 to 20 carbon atoms.

According to one embodiment of the present invention, the transition metal compound of Formula 1 is preferably a compound represented by the following Formula 2;

Where

R ₅ and R ₆ are hydrogen atoms; An alkyl group having 1 to 20 carbon atoms; Aryl groups having 6 to 30 carbon atoms; Or a silyl group having 0 to 20 carbon atoms;

R ₇ is an alkyl group having 1 to 20 carbon atoms; Aryl groups having 6 to 30 carbon atoms; Silyl groups having 0 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Alkylaryl groups having 7 to 30 carbon atoms; Or an arylalkyl group having 7 to 30 carbon atoms;

Q ₃ and Q ₄ are each independently a halogen atom; An alkyl group having 1 to 20 carbon atoms; Arylamido groups having 6 to 30 carbon atoms; Or an alkyl group having 1 to 20 carbon atoms;

M represents a Group 4 transition metal.

According to one embodiment of the invention, the transition metal compound is preferably represented by one of the formula 1a to 1e;

Where

R ₈ represents hydrogen or a methyl group, and Q ₅ and Q ₆ each independently represent a methyl group, a dimethylamido group or a chlorine atom.

The present invention is a transition metal compound of Formula 1; And at least one cocatalyst compound selected from the group consisting of compounds represented by Formula 3, Formula 4, and Formula 5; It provides a catalyst composition comprising:

_{- [Al (R 9) -O} ] a -

Wherein R ₉ is a halogen atom; Hydrocarbon groups having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom,

a represents an integer of 2 or more.

D (R ₉ ) ₃

Wherein D represents aluminum or boron,

R ₉ is a halogen atom; Hydrocarbon groups having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom.

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

Wherein L represents a neutral or cationic Lewis acid,

Z represents a Group 13 element,

A is at least one hydrogen atom halogen atom; Hydrocarbon groups having 1 to 20 carbon atoms; An alkyl group having 2 to 20 carbon atoms substituted with an alkoxy group or an aryloxy group; Or an aryl group having 7 to 30 carbon atoms substituted with an alkoxy group or an aryloxy group.

The present invention also includes the step of contacting the transition metal compound of Formula 1 with a compound represented by Formula 3 and / or Formula 4 to obtain a mixture, further comprising adding a compound represented by Formula 5 to the mixture It provides a method for producing a catalyst composition comprising a.

According to one embodiment of the present invention, the ratio of the compound represented by Formula 4 and the compound represented by Formula 5 to the transition metal compound of Formula 1 is preferably 1:20 to 500 and 1: 2 to 5, respectively. Do.

The present invention to achieve the above other technical problem,

Using the catalyst composition and the monomer, there is provided a method for producing an olefin polymer using a continuous solution process.

The continuous solution process consists of a catalytic process, a polymerization process, a solvent separation process and a recovery process, and a brief overview is as follows: The polymerization reaction in the reactor is performed at a temperature of 70 to 200 ° C. and a pressure of 50 to 100 bar. It is preferable to make. The solvent separation process is performed by changing the solution temperature and pressure to remove the solvent present with the polymer exiting the reactor. The polymer solution transferred from the reactor is heated to 230 ° C. through a heater to lower the pressure in the first separator to vaporize the solvent, and the pressure in the separator is preferably about 5 to 10 bar. The gasified solvent can be recycled.

According to one embodiment of the invention, the 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 and the like are preferred.

According to one embodiment of the invention, the monomers used to prepare the copolymer, ethylene; And at least one monomer selected from the group consisting of propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene.

Hereinafter, the present invention will be described in more detail.

The transition metal compound represented by the following Chemical Formula 1 according to the present invention has a phenylene bridge to facilitate access of a monomer having a large steric hindrance, and a stable five-membered ring structure can be stably maintained. Ultra low density polyolefin copolymers of less than 0.910 g / cc may be prepared using catalyst compositions comprising the compounds.

The present invention provides a transition metal compound of Formula 1 below.

<Formula 1>

In the above formula, R ₁ and R ₂ are each independently a hydrogen atom; Alkyl, aryl or silyl radicals having 1 to 20 carbon atoms; Alkenyl, alkylaryl, or arylalkyl radicals having 1 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; R ₁ and R ₂ may be linked to each other by an alkylidine radical comprising an alkyl or aryl radical having 1 to 20 carbon atoms to form a ring; Each R ₄ is independently a hydrogen atom; Halogen radicals; Or an alkyl or aryl radical having 1 to 20 carbon atoms, wherein R ₄ of the two R ₄ may be a folded ring structure connected with each other, and; R ₃ is an alkyl sulfonyl, aryl sulfonyl or silyl sulfonyl radical having 1 to 20 carbon atoms; Alkyl carbonyl, aryl carbonyl or silyl carbonyl radicals having 1 to 20 carbon atoms; Alkyl carboxy or aryl carboxy radicals having 1 to 20 carbon atoms; Or an alkyl phosphonyl or aryl phosphonyl radical having 1 to 20 carbon atoms; M is a Group 4 transition metal; Q ₁ and Q ₂ are each independently a halogen radical; Alkyl or aryl amido radicals having 1 to 20 carbon atoms; Alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals having 1 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.

In the transition metal compound represented by Chemical Formula 1 according to the present invention, the cyclopentadienyl derivative and the amido group are connected by a phenylene bridge, the Cp-MN angle is structurally narrow, and the Q ₁ -MQ ₂ angle at which the monomer approaches is In addition, unlike the CGC structure connected by the silicon bridge, Cp, the phenylene bridge, and nitrogen together with the metal sites have a stable and rigid five-membered ring structure. .

Therefore, when these compounds are reacted with methylaluminoxane or a cocatalyst such as B (C ₆ F ₅ ) ₃ to be activated and then applied to olefin polymerization, they exhibit characteristics such as high activity, high molecular weight and high copolymerization even at high polymerization temperatures. It will be possible to produce polyolefins having. In particular, due to the structural characteristics of the catalyst, as well as linear low density polyethylene having a density of 0.910 to 0.930 g / cc, as well as a large amount of alpha-olefins can be introduced, ultra low density polyolefin copolymers having a density of less than 0.910 g / cc can be prepared. . In addition, various substituents may be introduced into the cyclopentadienyl ring, the nitrogen, and the phenylene ring, which can ultimately easily control the structure and physical properties of the polyolefin produced by easily controlling the electronic and three-dimensional environment around the metal. It means that there is.

The compound of formula 1 according to the present invention is preferably used to prepare a catalyst for the polymerization of olefin monomers, but is not limited thereto, and other applications can be applied to all fields in which the transition metal compound can be used.

In the compound of Chemical Formula 1 according to the present invention, compounds represented by the following Chemical Formula 2 are preferred as compounds that are more preferred for controlling the electronic and three-dimensional environment around the metal.

<Formula 2>

Where

R ₅ and R ₆ are hydrogen atoms; Or alkyl, aryl or silyl radical of 1 to 20 carbon atoms;

R ₇ is an alkyl, aryl or silyl radical having 1 to 20 carbon atoms; Alkenyl, alkylaryl, or arylalkyl radicals having 1 to 20 carbon atoms;

Q ₃ and Q ₄ are each independently a halogen radical; Alkyl or aryl amido radicals having 1 to 20 carbon atoms; Or an alkyl radical having 1 to 20 carbon atoms;

M is as defined above.

According to one embodiment of the present invention, the transition metal compound of Chemical Formula 1 is preferably represented by one of the following Chemical Formulas 1a to 1e;

<Formula 1a>

<Formula 1b>

<Formula 1c>

<Formula 1d>

<Formula 1e>

In the above,

R ₈ is selected from hydrogen or methyl radicals, and Q ₅ and Q ₆ are each independently selected from methyl, dimethylamido or chloride radicals.

The present invention provides an activated catalyst composition comprising a compound of Formula 1 and a promoter compound represented by a compound of Formulas 3 to 5, and the like. Such catalyst compositions can be used for olefin single (co) polymerization.

<Formula 3>

_{- [Al (R 9) -O} ] a -

Wherein each R ₉ is independently a halogen radical; Hydrocarbyl radicals having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;

<Formula 4>

D (R ₉ ) ₃

Wherein D is aluminum or boron; Each R ₉ is independently as defined above;

<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 each independently an aryl or alkyl radical having 6 to 20 carbon atoms in which one or more hydrogen atoms are replaced by halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy radicals.

As a method of preparing the catalyst composition, the present invention comprises the steps of: first contacting a transition metal compound of Formula 1 with a compound represented by Formula 3 and / or Formula 4 to obtain a mixture; And it provides a manufacturing method comprising the step of adding a compound represented by the formula (5) to the mixture.

On the contrary, a method of preparing a catalyst composition is provided by contacting a transition metal compound of Formula 1 with a compound represented by Formula 3.

In the case of the first method of preparing the catalyst composition, the weight ratio of the transition metal compound of Formula 1 to the compound of Formula 3 and / or Formula 4 is 1: 2 to 5000, preferably 1:10 to 1000, More preferably, it is 1: 20-500. When the weight ratio of the compound of Formula 3 and / or Formula 4 to the transition metal compound of Formula 1 is less than 1: 2, there is a problem that the alkylation of the metal compound may not proceed sufficiently due to the small amount of alkylating agent, and 1: 5000 When exceeded, the alkylation of the metal compound is made, but there is a problem that the activation of the alkylated metal compound is difficult to be completely made due to the side reaction between the remaining excess alkylating agent and the activator of Formula 5.

In a first method of preparing the catalyst composition, the weight ratio of the compound of Formula 5 to the transition metal compound of Formula 1 is 1: 1 to 25, preferably 1: 1 to 10, more preferably 1: 2 To 5; When the ratio of the compound represented by Chemical Formula 5 to the transition metal compound of Chemical Formula 1 is less than 1: 1, the amount of the activator is relatively small, so that the activity of the catalyst composition that is not fully activated due to the inactivation of the metal compound is poor. In the case of exceeding 1:25, the activation of the metal compound is completely performed, but it is not preferable because the excess cost of the remaining activator may cause the cost of the catalyst composition to be uneconomical or the purity of the polymer to be produced is poor.

In the second method of preparing the catalyst composition, the molar ratio of the compound represented by Formula 3 to the transition metal compound of Formula 1 is 1:10 to 10000, preferably 1: 100 to 5000, more preferably Is 1: 500 to 2000. When the molar ratio is less than 1:10, the amount of the activator is relatively small, so that the activation of the metal compound is not completed, and thus the activity of the resulting catalyst composition is inferior. When the molar ratio exceeds 1: 10000, the activation of the metal compound Although completely made, there is a problem that the cost of the catalyst composition is not economically low or the purity of the resulting polymer is inferior with the remaining excess activator.

Hydrocarbon solvents such as pentane, hexane, heptane and the like as a reaction solvent in the preparation of the activation composition; Or aromatic solvents such as benzene, toluene, and the like. The transition metal compounds and cocatalyst of the formula (1) can also be used in the form supported on silica or alumina.

Examples of the compound represented by Formula 3 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like, and a preferable compound is methyl aluminoxane.

Examples of the alkyl metal compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclo Pentyl 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 , Trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound of Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, Trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-tripololomethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentaflo Rophenylboron, N, N-diethylamyldium tetrapetylboron, N, N-diethylanilidedium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium Tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium Niumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (p-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum , Tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylaniyl Linium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenylphosphonium Tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetrape Nyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p-tolyl) boron, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o, p-dimethylphenyl) boron, trimethyl Ammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluoro Phenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetra Pentafluorophenylboron, triphenylphosphonium tetraphenylboron, triphenylcarbonium tetra (p-tripulomethylphenyl) boron, triphenylcarbonium tetrapentafluorophenyl boron, and the like.

The present invention also provides a method of preparing a polyolefin homopolymer or copolymer by contacting a catalyst composition comprising the compound of Formula 1 and at least one compound selected from compounds represented by Formulas 3 to 5 with at least one olefin monomer. To provide.

The most preferred polymerization process using the activating composition 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.

The continuous solution polymerization process of the present invention is composed of a catalytic process, a polymerization process, a solvent separation process, and a recovery process step.

a) catalytic process

The activated compositions of the present invention are aliphatic hydrocarbon solvents having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example pentane, hexane, heptane, nonane, decane, and their isomers and aromatic hydrocarbon solvents such as toluene, benzene, dichloromethane, It can be injected by dissolving or diluting in a hydrocarbon solvent substituted with a chlorine atom 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 additionally using a promoter.

b) polymerization process

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. In particular, the activating composition of the present invention has a high molecular weight in the copolymerization reaction of monomers having high steric hindrance such as ethylene and 1-octene even at a high reaction temperature of 90 ° C. or higher, and the preparation of an ultra low density copolymer having a polymer density of 0.910 g / cc or less Has the feature that it is possible.

More specifically, the monomer constituting the copolymer is preferably at least one monomer selected from the group consisting of ethylene and propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene. .

Polymerization solvents of the present invention include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms suitable for the olefin polymerization process, such as pentane, hexane, heptane, nonane, decane, and their isomers and aromatic hydrocarbon solvents such as toluene and benzene, dichloro Hydrocarbon solvents substituted with chlorine atoms such as methane, chlorobenzene and the like. The solvent used here is preferably used by removing a small amount of water, air or the like acting as a catalyst poison by treating with a small amount of alkylaluminum.

The solvent is introduced into the reactor at a temperature of -40 to 150 ° C. using a heater or a freezer and the polymerization is started with the monomer and the activating composition. Feeds to the reactor are passed through the mixture without additional pumping between the reactor arrangement, the pressure reducing means and the separator by means of a high capacity pump raising the feed pressure above 50 bar and feeding it through the movement of the pump. It is preferable that the polymerization reaction temperature in a reactor consists of a temperature of 70-200 degreeC, More preferably, it is 90-150 degreeC. In the course of the polymerization reaction, the pressure in the reactor is preferably 50 to 100 bar, more preferably about 60 to 90 bar. The polymer reacted in the reactor is maintained at a concentration of less than 20 wt% in the solvent and is passed to the first solvent separation process for solvent removal after a short residence time. The residence time of the polymer in the reactor is preferably 5 minutes to 30 minutes.

c) solvent separation process

The solvent separation process is performed by changing the solution temperature and pressure to remove the solvent present with the polymer. The solvent separation process is performed by varying the solution temperature and pressure to remove the solvent present with the polymer exiting the reactor. The polymer solution transferred from the reactor was heated to 230 ° C. through a heater, and then the pressure was lowered through a pressure drop device to vaporize the solvent in the first separator. At this time, the pressure in the separator is preferably about 5 to 10 bar, more preferably 7 to 8 bar. The temperature in the separator is preferably between 200 and 250 ° C., but most preferably 230 ° C. The solvent gasified 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 the 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 cutter. The solvent and other unreacted monomers vaporized in the second separation process can be sent to a recovery process for reuse after purification.

d) recovery process

The organic solvent added to the polymerization process together with the raw material may be recycled to the polymerization process with 85% of the unreacted raw material in the primary solvent separation process. However, 15% of 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. It is good to be reused after purification.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these Examples are only for illustrating the present invention and the present invention is not limited to these.

Synthesis of Ligands and Metal Compounds

Organic reagents and solvents were purchased from Aldrich and Merck and purified by standard methods. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment. To verify the structure of the compound, spectra and diagrams can be obtained using 400 MHz nuclear magnetic resonance (NMR) and X-ray spectroscopy, respectively.

Example 1: Preparation of Phenylene (cyclohexylamido) (2,3,5-trimethylcyclopentadienyl) titanium dimethyl

TiCl ₄ ^. Add DME (0.200 g, 0.715 mmol) and diethyl ether (5 mL), cool to −30 ° C., add MeLi (0.654 g, 1.430 mmol, dissolved in 1.6 M diethyl ether) solution, and stir for 15 minutes. . Phenylene (cyclohexyl amido) (2,3,5-trimethylcyclopentadienyl) diridium salt (0.252 g, 0.715 mmol) is added to the solution and reacted at room temperature for 3 hours. Removal of volatiles, extraction with pentane (7 mL) and vacuum drying yielded a dark red oil (0.211 g, 83%). Analysis of the present compounds from the ¹ H and ¹³ C NMR spectra can confirm their presence.

Comparative Example 1: Preparation of Dimethylsilyl (t-butylamido) (tetramethylcyclopentadienyl) titanium dichloride

The titanium metal compound was purchased from Boulder Scientific in USA and used for the ethylene copolymerization reaction.

Example 2: Copolymerization of Ethylene and 1-Octene by Continuous Solution Process

In a 1 L continuous stirred reactor preheated to 100 ° C., hexane (5.0 kg / h) solvent and 1-octene (0.78 kg / h) and ethylene monomer (0.5 kg / h) are fed at a pressure of 60 bar. Metal compound of Example 1 (1.6 μmol / min, Al / Ti = 25) and octadecylmethylammonium tetrakis (pentafluorophenyl) borate (4.8 μmol /) treated with triisobutylaluminum compound from catalyst storage tank min) A cocatalyst is fed to the reactor to proceed with the copolymerization reaction. The polymer solution formed by the copolymerization reaction is depressurized to 7 bar at the rear of the reactor, and then sent to a solvent separator preheated to 230 ° C. to remove most of the solvent by a solvent separation process. The copolymer sent to the second separator by the pump completely removes the residual solvent by a vacuum pump, and then passes through the cooling water and the cutter to obtain the granulated polymer.

Example 3: Copolymerization of Ethylene and 1-Octene by Continuous Solution Process

1-octene (0.5-1.5 kg / h), polymerization temperature (90-150 ° C.) and metal compound (1) using a metal compound of Example 1 in hexane (5 kg / h) solvent in a 1 L continuous stirred reactor Ethylene copolymerization was carried out in the same manner as in Example 2 according to the change of 0.96 to 3.2 μmol / min).

Physical property evaluation (weight, activity, melt index, melting point, density)

The melt index (Melt Index, MI) of the polymer was measured by ASTM D-1238 (Condition E, 190 ° C., 2.16 Kg load). The melting point (T _m ) of the polymer was obtained by using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 2920). That is, the temperature was increased to 200 ° C., then maintained at that temperature for 5 minutes, then lowered to 30 ° C., and the temperature was increased again to form the melting point of the DSC curve. At this time, the rate of temperature rise and fall is 10 ° C./min, and a melting point is obtained while the second temperature rises.

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

Experimental Example 1

According to the experimental method, various physical properties of the copolymer obtained in the copolymerization of Examples 2 and 3 using the transition metal compounds of Example 1 and Comparative Example 1 were shown in Table 1 below.

TABLE 1

Ethylene and 1-octene copolymerization result

Used complex 1-octene (kg / h) Metal compound (g) Polymerization temperature (℃) Melt Index ^a (g / 10min) Melting point (℃) Density (g / cc) Example 1 0.78 1.6 112 0.05 67, 112 0.883 Example 1 1.17 1.6 107 0.07 54, 108 0.873 Example 1 1.33 1.6 115 0.06 56, 108 0.882 Example 1 1.33 1.6 107 0.09 48, 107 0.872 Comparative Example 1 0.78 0.8 128 1.17 88 0.889 Comparative Example 1 1.17 0.8 136 0.30 99 0.897 Comparative Example 1 1.17 0.8 130 0.58 98 0.892 Comparative Example 1 1.17 0.8 133 0.23 86 0.892 Comparative Example 1 1.33 0.8 132 1.28 80 0.884

a: I ₂ value

As shown in Table 1, when the compound of Example 1 of the present invention is used, the density is all lower at the same octene concentration as compared to the polymerization result using Comparative Example 1, and it can be seen that most of them show high copolymerization reactivity. The compound according to Example 1 is capable of preparing a copolymer having a lower density than that of Comparative Example 1 in all conditions compared to Comparative Example 1, which indicates that the reactivity with respect to a sterically hindered olefin monomer such as 1-octene is excellent. .

In addition, in the case of the compound of Example 1, it can be seen that all have a lower melt index value than the compound of Comparative Example 1, which means that the compound of Example 1 has a higher average molecular weight value than the compound of Comparative Example 1 It also indicates that the compound of Example 1 is more advantageous for the production of high molecular weight compounds than the compound of Comparative Example 1.

The transition metal compound according to the present invention has a phenylene bridge, unlike conventional transition metal compounds having a silicon bridge and an oxido ligand, and thus the monomer structure is more easily accessible, and the robust five-membered ring structure can be stably maintained. In the continuous solution polymerization process using the catalyst composition containing the transition metal compound, it is possible to prepare a variety of copolymers at a wide range of temperatures and pressures. It is possible to produce ultra low density polyolefin copolymers of less than g / cc.

Claims (18)

delete delete delete A transition metal compound of Formula 1; And at least one cocatalyst compound selected from the group consisting of compounds of Formulas 3, 4 and 5; Catalyst composition comprising: <Formula 1>

Where R ₁ and R ₂ are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; Aryl groups having 6 to 30 carbon atoms; Silyl groups having 0 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Alkylaryl groups having 7 to 30 carbon atoms; Arylalkyl groups having 7 to 30 carbon atoms; A metalloid radical of a Group 14 metal substituted with a hydrocarbon group; R ₁ and R ₂ may be linked to each other by an alkylidene group having 2 to 30 carbon atoms substituted with an alkyl group and an aryl group to form a ring; Each R ₄ is independently a hydrogen atom; Halogen atom; An alkyl group having 1 to 20 carbon atoms; It represents a group having a carbon number of 6 to 30 aryl, wherein R ₄ of the two R ₄ may be a folded ring (fused ring) structure are connected to each other, and; R ₃ is an alkylsulfonyl group having 1 to 20 carbon atoms; Arylsulfonyl group having 6 to 30 carbon atoms; Silylsulfonyl groups having 0 to 20 carbon atoms; An alkylcarbonyl group having 1 to 20 carbon atoms; Arylcarbonyl group having 7 to 30 carbon atoms; Silylcarbonyl groups having 1 to 20 carbon atoms; Alkyl carboxyl groups having 2 to 20 carbon atoms; Aryl carboxy groups having 7 to 30 carbon atoms; Alkyl phosphonyl groups having 1 to 20 carbon atoms; An arylphosphonyl group having 6 to 30 carbon atoms; M represents a Group 4 transition metal; Q ₁ and Q ₂ are each independently a halogen atom; An alkyl group having 1 to 20 carbon atoms; Arylamido groups having 6 to 30 carbon atoms; An alkyl group having 1 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Aryl groups having 6 to 30 carbon atoms; Alkylaryl groups having 7 to 30 carbon atoms; Arylalkyl groups having 7 to 30 carbon atoms; Or an alkylidene group having 1 to 20 carbon atoms; <Formula 3> _{- [Al (R 9) -O} ] a - Wherein R ₉ is a halogen atom; Hydrocarbon groups having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, a represents an integer of 2 or more; <Formula 4> D (R ₉ ) ₃ Wherein D represents aluminum or boron, R ₉ is a halogen atom; Hydrocarbon groups having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen atoms; <Formula 5> _{^{[LH] + [ZA 4]}} - or _{^{[L] + [ZA 4]}} - Wherein L represents a neutral or cationic Lewis acid, Z represents a Group 13 element, A is at least one hydrogen atom halogen atom; Hydrocarbon groups having 1 to 20 carbon atoms; An aryl or alkyl radical having 6 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 30 carbon atoms. The catalyst composition according to claim 4, wherein the weight ratio of the compound of Formulas 3 and 4 to the transition metal compound of Formula 1 is 1: 2 to 5000. 5. The catalyst composition of claim 4, wherein the weight ratio of the compound of Formula 5 to the transition metal compound of Formula 1 is 1: 1 to 25. 6. The catalyst composition of claim 4, wherein the compound of formula 3 is methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane. According to claim 4, wherein the compound of formula 4 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclo Pentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide , Trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and a more preferable compound is trimethylaluminum, triethylaluminum, or triisobutylaluminum. According to claim 4, wherein the compound of formula 5 is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p- Tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-tripolomethylmethyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium Umtetrapentafluorophenylboron, N, N-diethylamyldium tetrapetyl boron, N, N-diethylanilidedium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, Diethyl ammonium tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, t Methylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl Aluminum, tributyl ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethyl ammonium tetra (p-trifluoromethylphenyl) aluminum, tributyl ammonium tetrapentafluorophenylaluminum, N, N-diethyl anyl Linium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenylphosphonium Tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium Tetraphenylboron, tripropylammonium tetraphenylboron, 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 tetrapentaflo Rophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium Tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, triphenylcarbonium tetra (p-tripulomethylphenyl) boron, or triphenylcarbonium tetrapentafluorophenyl boron Composition. A method of preparing a catalyst composition comprising: contacting at least one compound selected from the group consisting of a compound of Formula 3 and a compound of Formula 4 with a transition metal compound of Formula 1 in a reaction solvent: <Formula 1>

Where R ₁ and R ₂ are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; Aryl groups having 6 to 30 carbon atoms; Silyl groups having 0 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Alkylaryl groups having 7 to 30 carbon atoms; Arylalkyl groups having 7 to 30 carbon atoms; A metalloid radical of a Group 14 metal substituted with a hydrocarbon group; R ₁ and R ₂ may be linked to each other by an alkyl group and an alkylidene group having 1 to 30 carbon atoms substituted with an aryl group to form a ring; Each R ₄ is independently a hydrogen atom; Halogen atom; An alkyl group having 1 to 20 carbon atoms; It represents a group having a carbon number of 6 to 30 aryl, wherein R ₄ of the two R ₄ may be a folded ring (fused ring) structure are connected to each other, and; R ₃ is an alkylsulfonyl group having 1 to 20 carbon atoms; Arylsulfonyl group having 6 to 30 carbon atoms; Silylsulfonyl groups having 0 to 20 carbon atoms; An alkylcarbonyl group having 1 to 20 carbon atoms; Arylcarbonyl group having 7 to 30 carbon atoms; Silylcarbonyl groups having 1 to 20 carbon atoms; Alkyl carboxyl groups having 2 to 20 carbon atoms; Aryl carboxy groups having 7 to 30 carbon atoms; Alkyl phosphonyl groups having 1 to 20 carbon atoms; An arylphosphonyl group having 6 to 30 carbon atoms; M represents a Group 4 transition metal; Q ₁ and Q ₂ are each independently a halogen atom; An alkyl group having 1 to 20 carbon atoms; Arylamido groups having 6 to 30 carbon atoms; An alkyl group having 1 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Aryl groups having 6 to 30 carbon atoms; Alkylaryl groups having 7 to 30 carbon atoms; Arylalkyl groups having 7 to 30 carbon atoms; Or an alkylidene group having 1 to 20 carbon atoms; <Formula 3> _{- [Al (R 9) -O} ] a - Wherein R ₉ is a halogen atom; Hydrocarbon groups having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, a represents an integer of 2 or more; <Formula 4> D (R ₉ ) ₃ Wherein D represents aluminum or boron, R ₉ is a halogen atom; Hydrocarbon groups having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom. The method of claim 10, further comprising adding a compound of formula (5): <Formula 5> _{^{[LH] + [ZA 4]}} - or _{^{[L] + [ZA 4]}} - Wherein L represents a neutral or cationic Lewis acid, Z represents a Group 13 element, A is at least one hydrogen atom halogen atom; Hydrocarbon groups having 1 to 20 carbon atoms; An aryl or alkyl radical having 6 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 30 carbon atoms. The method of claim 10, wherein the reaction solvent is a hydrocarbon solvent or an aromatic solvent. The method for preparing a catalyst composition according to claim 10 or 11, wherein the transition metal compound of Formula 1 and the compound of Formulas 3 to 5 are supported on silica or alumina. Dissolving or diluting the catalyst composition according to claim 4 in a reaction solvent into the reactor; And And polymerizing the polymerizable monomer into the reactor. The method of claim 13, wherein the polymerizable monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-ounde Sen, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-atocene, norbornene, norbonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1, Preparation of an olefin polymer characterized by 4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene or a mixture of two or more thereof. Way. The method of claim 13, wherein the polymerizable monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-ounde A method for producing an olefin polymer, characterized in that at least one selected from the group consisting of sen, 1-dodecene, 1- tetradecene, 1- hexadecene and 1- itocene. The method of claim 13, wherein the olefin polymer is at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene and 1-octene. The method for preparing an olefin polymer according to claim 13, further comprising separating the solvent from the obtained polymer solution and recovering it.