KR102561337B1 - Metal complex, catalysts composition comprising the metal complex and preparation method of ethylene-alpha-olefin / diene copolymer - Google Patents

Abstract

The present invention relates to a metal catalyst composition used in the synthesis of an ethylene/alpha-olefin/diene copolymer having high molecular weight and low density according to improved physical properties and a method for preparing the ethylene/alpha-olefin/diene copolymer using the same.

Description

A metal complex, a metal catalyst composition containing the metal complex, and a method for preparing a copolymer containing ethylene, alpha-olefin and diene using the metal catalyst composition ALPHA-OLEFIN/DIENE COPOLYMER}

The present invention relates to a metal complex, a metal catalyst composition containing the metal complex, and a method for preparing a copolymer containing ethylene, an alpha-olefin and a diene using the metal catalyst composition, It relates to a catalyst composition used in synthesis and a method for preparing a copolymer using the same.

The tertiary copolymer of ethylene, alpha-olefin, and diene has a molecular structure without unsaturated bonds in the main chain, and has weather resistance, chemical resistance, and heat resistance superior to general conjugated diene rubber. Due to these characteristics, tertiary elastic copolymers are widely used in various automobile parts materials, wire materials, construction and industrial materials such as various hoses, gaskets, belts, bumpers, or blends with plastics.

Previously, such tertiary copolymers such as rubber have been prepared by copolymerizing three types of monomers using a catalyst mainly containing a vanadium compound, for example, a vanadium-based Ziegler-Natta catalyst or a metallocene catalyst.

Studies on catalysts for polymerization of the copolymer have been conducted with much focus on accurately understanding the relationship between characteristics of the catalyst system, that is, structure, activity, and selectivity.

However, in the polymerization process of copolymers in which alpha-olefins having 4 or more carbon atoms are applied, not much is known about stabilized catalysts that can actually be applied to commercial processes. Accordingly, higher polymerization performance can be realized and excellent There is still a need for research on catalysts capable of providing copolymers with physical properties.

In order to solve the above problems, the present invention provides a novel metal complex, a metal catalyst composition containing the metal complex, and a method for preparing a copolymer containing ethylene, alpha-olefin and diene using the metal catalyst composition. The purpose.

However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

In order to solve the above problems, the present invention provides a novel metal complex, a metal catalyst composition containing the metal complex, and a method for preparing a copolymer containing ethylene, alpha-olefin and diene using the metal catalyst composition. The purpose.

However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

According to one embodiment of the present invention, the metal complex according to the present invention is represented by Formula 1 below.

[Formula 1]

In Formula 1,

M corresponds to a Group 4 metal,

A, B, C are organic ligand systems containing from 1 to 40 atoms that are not hydrogen;

X is a halogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, or a substituted aryl group.

In addition, according to another embodiment of the present invention, the metal complex according to the present invention is represented by Formula 2 below.

[Formula 2]

In Formula 2,

M corresponds to a Group 4 metal,

A, B are organic ligand systems containing 1 to 40 atoms other than hydrogen;

X is a halogen, an alkyl group having 1 to 10 carbon atoms, an aryl group or a substituted aryl group, and n is 2 or 3.

In addition, the present invention provides a method for producing an ethylene / alpha-olefin / diene copolymer comprising contacting ethylene, an alpha-olefin having at least 4 or more carbon atoms, and a diene monomer with a catalyst composition containing any one of the above metal complexes do.

The novel metal complex according to the present invention and the catalyst composition including the same have excellent effects capable of preparing an ethylene/alpha-olefin/diene copolymer having a high molecular weight and a low density according to improved physical properties.

Advantages and features of the present invention, and methods of achieving them, will become clear with reference to the detailed description of the following embodiments taken in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below and will be implemented in various forms different from each other, only these embodiments make the disclosure of the present invention complete, and common knowledge in the art to which the present invention pertains. It is provided to completely inform the person who has the scope of the invention, and the present invention is only defined by the scope of the claims.

First, the metal complex according to the present invention will be described in detail.

A metal complex according to an embodiment of the present invention is represented by Formula 1 below.

[Formula 1]

In Formula 1, M corresponds to a Group 4 metal, A, B, and C are organic ligand systems containing 1 to 40 atoms other than hydrogen, and X is a halogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group. or a substituted aryl group. In particular, the M may be any one of Ti, Zr, and Hf among Group 4 metals, preferably Hf.

In addition, any one of A, B, and C is a chelated ligand including a hetero atom or a hetero ring, and the hetero atom is preferably any one of N, O, and P.

In addition, the A, B, and C may be bonded to the central metal M through a covalent bond or a coordinate bond, and the A, B, and C may be bonded to the central metal M together or individually.

As such, preferred examples of the metal complex according to Chemical Formula 1 may be represented by Chemical Formula 5 or Chemical Formula 6 below.

[Formula 5]

[Formula 6]

In Chemical Formulas 5 and 6, Me means a methyl group, and I-Pr means an isopropyl group.

In addition, a metal complex according to another embodiment of the present invention is represented by Chemical Formula 2 below.

[Formula 2]

In Formula 2, M corresponds to a Group 4 metal, A and B are organic ligand systems containing 1 to 40 atoms other than hydrogen, and X is a halogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, or a substituted aryl group, and n is 2 or 3.

In particular, the M may be any one of Ti, Zr, and Hf among Group 4 metals, preferably Hf.

In addition, any one of A and B is a chelated ligand including a hetero atom or a hetero ring, and the hetero atom is preferably any one of N, O and P.

In addition, when n is 2, A and B may be bonded to the central metal M through a covalent bond, and when n is 3, one of A and B may be bonded to the central metal M through a coordination bond. can be coupled to In addition, A and B may be bonded together or individually to the central metal M.

When n is 3, the metal complex according to Formula 2 may be represented by Formula 3 below.

[Formula 3]

In addition, a preferable example of the metal complex according to Chemical Formula 3 may be represented by Chemical Formula 7 below.

[Formula 7]

In Formula 7, Me means a methyl group, and Bn means a benzyl group.

When n is 2 in Formula 2, the metal complex according to Formula 2 may be represented by Formula 4 below.

[Formula 4]

In addition, preferred examples of the metal complex according to Chemical Formula 4 may be represented by Chemical Formula 8 or Chemical Formula 9 below.

[Formula 8]

[Formula 9]

In Formula 8 or Formula 9, Me means a methyl group.

Next, the present invention provides a metal catalyst composition comprising the metal complex described above. The metal catalyst composition may include the above-described metal complex and a cocatalyst that functions to make the metal complex an active catalyst component. Examples of the cocatalyst include an aluminum compound or a boron compound, but are not limited thereto.

Next, the present invention provides a method for producing an ethylene/alpha-olefin/diene copolymer comprising contacting an alpha-olefin having at least 4 or more carbon atoms and a diene monomer with the metal catalyst composition described above.

Here, as the copolymer comprising ethylene, alpha-olefin and diene monomer according to the present invention, alpha-olefin having at least 4 or more carbon atoms is used. Representative examples of tertiary elastic copolymers containing ethylene, alpha-olefin and diene monomers include EPDM rubber, which is a copolymer of ethylene, propylene and diene. Alpha-olefins having at least 4 or more carbon atoms are used to provide.

Preferably, the alpha-olefin may include at least one of alpha-olefins having 6 and 8 carbon atoms, 1-hexene may be used as the alpha-olefin having 6 carbon atoms, and alpha-olefins having 8 carbon atoms 1-octene may be used as the olefin.

In addition, non-conjugated diene-based monomers may be used as the diene monomer included in the copolymer according to the present invention. Specific examples thereof include 5-1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12-tetradecadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl -1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-hepta Diene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl- 1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene , 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1 ,6-octadiene, 7-methyl-1,6-octadiene, 4-methyl-1,4-nonadiene, ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-(2- Propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene, 5-(4-pentenyl)- 2-norbornene, 5-(1-methyl-3-butenyl) -2-norbornene, 5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl) - 2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, 5-(2-ethyl-3-butenyl)-2-norbornene, 5-(6-heptenyl) ) -2-norbornene, 5-(3-methyl-hexenyl)-2-norbornene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornene, 5-(3-ethyl- 4-pentenyl) -2-norbornene, 5-(7-octenyl) -2-norbornene, 5-(2-methyl-6-heptenyl) -2-norbornene, 5-(1,2- Dimethyl-5-hexenyl) -2-norbornene, 5-(5-ethyl-5-hexenyl) -2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl) -2- Norbornene, 5-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-butylidene-2-norbornene, 5-isobutylidene-2-norbornene, 2,3- diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, etc., and the diene selected from these is 1 More than one species can be used.

As described above, the copolymer according to the present invention is selected from an alpha-olefin having at least 4 carbon atoms and contains 40 to 80% by weight of ethylene, 15 to 80% by weight, under a catalyst composition comprising a metal complex represented by Chemical Formulas 1 to 3. It can be prepared by copolymerizing a monomer composition containing 55% by weight of an alpha-olefin and 0.5 to 15% by weight of a diene while continuously feeding it to a reactor.

[catalyst Synthesis Example 1 ]

The synthesis process of Catalyst Synthesis Example 1 is shown as the following formula, and Catalyst Synthesis Example 1 is the same as the metal complex according to Formula 5 mentioned above.

[Formula: Synthesis of Catalyst Synthesis Example 1]

The synthesis process of Catalyst Synthesis Example 1 is specifically described below.

Within a nitrogen-filled glove box, a glass bottle was filled with ligand 1 (5.1 g, 9.9 mmol) dissolved in 50 mL of toluene. To this solution, nBuLi (4.2 mL of 2.5 M hexane solution, 10.5 mmol) was added using a syringe. This solution was stirred for 1 h, then solid HfCl4 (3.2 g, 10.00 mmol) was added. The vessel was capped with an air-cooled reflux condenser and heated at 100° C. for 2 hours. After cooling, MeMgBr (11.6 mL of a 3 M solution in diethyl ether, 34.9 mmol, 3.5 equiv) was added by syringe and the resulting mixture was stirred overnight at ambient temperature. The solvent was removed from the reaction mixture using a vacuum system attached to the drying box. Toluene was added to the residue and the mixture was filtered. The residue was washed with additional toluene (8 washes with 50 mL until the eluent stream was colorless). The recovered eluent was removed by drying under vacuum, hexane (30 mL) was added and then removed by vacuum. Hexanes (50 mL) was added again and the resulting slurry was stirred for 30 minutes. The suspension was filtered and the collected product was washed with cold hexanes (50 mL) to give the desired product as a light yellow powder (5.6 g, 78%).

[catalyst Synthesis Example 2 ]

The synthesis process of Catalyst Synthesis Example 2 is shown in the following formula, and Catalyst Synthesis Example 2 is the same as the metal complex according to Formula 6 mentioned above.

[Formula: Synthesis of Catalyst Synthesis Example 2]

The synthesis process of Catalyst Synthesis Example 2 is specifically described below.

Ligand 2 (2.6 g, 5.0 mmol) dissolved in 20 mL of toluene was filled in a glass bottle in a nitrogen-filled glove box. To this solution was added nBuLi (2.1 mL of 2.5 M solution in hexane, 5.9 mmol) by syringe. The solution was stirred for 1 h, then solid HfCl4 (1.6 g, 5.00 mmol) was added. The vessel was capped with an air-cooled reflux condenser and heated at 100° C. for 2 hours. After cooling, MeMgBr (5.8 mL of diethyl ether 3M solution, 17.5 mmol, 3.5 equiv) was added by syringe and the resulting mixture was stirred overnight at ambient temperature. The solvent was removed from the reaction mixture using a vacuum system attached to the drying box. Toluene was added to the residue and the mixture was filtered. The residue was washed with additional toluene (8 washes with 50 mL until the eluent stream was colorless). The recovered eluent was removed by drying under vacuum, hexane (30 mL) was added and then removed by vacuum. Pentane (15 mL) was added again and the resulting slurry was stirred for 30 minutes. The suspension was filtered and the collected product was washed with cold pentane (20 mL) to give the desired product as a light yellow powder (2.5 g, 73%).

[catalyst Synthesis Example 3 ]

The synthesis process of Catalyst Synthesis Example 3 is shown as the following formula, and Catalyst Synthesis Example 3 is the same as the metal complex according to Formula 7 mentioned above.

[Formula: Synthesis of Catalyst Synthesis Example 3]

The synthesis process of Catalyst Synthesis Example 3 is specifically described below.

A solution of ligand 3 (0.206 g, 0.830 mmol) in toluene (5 mL) was cooled to -40 °C and then added to a vial containing HfBn4 (0.425 g, 0.783 mmol). The resulting solution immediately turned red, warmed to room temperature and stirred for 1 hour. The volume of toluene was reduced to approximately 2 mL, hexane (ca. 8 mL) was added and the solution was cooled to -40 °C. After 1 day, the resulting red crystals were collected and dried under vacuum to obtain the desired product in high purity (0.390 g, 71%).

[catalyst Synthesis Example 4 ]

The synthesis process of Catalyst Synthesis Example 4 is shown in the following formula, and Catalyst Synthesis Example 4 is the same as the metal complex according to Formula 8 mentioned above.

[Formula: Synthesis of Catalyst Synthesis Example 4]

The synthesis process of Catalyst Synthesis Example 4 is specifically described below.

A solution of Ligand 4 (0.300 g, 0.935 mmol) in toluene (5 mL) was added to a vial containing HfCl4 (0.300 g, 0.935 mmol). The resulting solution was heated to 50 °C and stirred for 1 hour. The reaction mixture was filtered and the filtrate was cooled to -40 °C. After 1 day, the resulting crystals were collected and dried under vacuum to obtain the desired product in high purity (0.126 g, 26%).

[catalyst Synthesis Example 5 ]

The synthesis process of Catalyst Synthesis Example 5 is shown as the following formula, and Catalyst Synthesis Example 5 is the same as the metal complex according to Formula 9 mentioned above.

[Formula: Synthesis of Catalyst Synthesis Example 5]

The synthesis process of Catalyst Synthesis Example 5 is specifically described below.

A solution of ligand 5 (0.300 g, 1.247 mmol) in toluene (5 mL) was added to a vial containing HfCl4 (0.376 g, 1.247 mmol). The resulting solution was heated to 50 °C and stirred for 1 hour. The reaction mixture was filtered and the filtrate was cooled to -40 °C. After 1 day, the resulting crystals were collected and dried under vacuum to obtain the desired product in high purity (0.171 g, 30%).

Example 1 to 9: EODM polymerization

A 3 L reactor was charged with 1400 mL of methyl cyclohexane. 1000 μmol of mMAO was added to the reactor using a cannula under N ₂ atmosphere, and then ENB was added in the amount shown in Table 1 below. The reactor was fed with 400 g (3.56 mol) of 1-octene. The temperature of the reactor was raised while ethylene was supplied to the reactor. Ethylene pressure was adjusted to 20 bar at 100 °C. 5 μmol of catalyst and 50 μmol of activator trityl tetrakis(pentafluorophenyl) borate (TTB) were diluted with 5 ml of toluene and transferred to a separate port attached to the reactor system. Subsequently, after supplying TTB to the reactor, a metal complex according to Catalyst Synthesis Example 1 (Formula 5) was supplied. Polymerization started immediately as the catalyst entered the reactor system. Polymerization was conducted for 10 min, and the viscous polymer solution was collected in a pot containing ethanol as a quenching agent. The polymer solution was then dried under vacuum to give the product. The products were then characterized for comonomer content and molecular weight.

The physical properties of the polymer according to each example are shown in the table below.

[Table 1]: EODM polymerization data

As can be seen from the polymerization DATA of Examples 1 to 9 above, the copolymer polymerized using the catalyst according to the present invention has a low density and a high molecular weight (M _w ). It can be seen that it has new and improved physical properties compared to the copolymer.

The above has been described with reference to the embodiments of the present invention, but these are merely examples, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. .

Therefore, the true technical protection scope of the present invention will be determined by the claims described below.

Claims (12)

delete A metal complex of Formula 2 below.

[Formula 2]

In Formula 2,
M corresponds to a Group 4 metal,
A, B are organic ligand systems containing 1 to 40 atoms other than hydrogen;
X is a halogen, an alkyl group having 1 to 10 carbon atoms, an aryl group or a substituted aryl group, and n is 2 or 3.
According to claim 2,
The M is a metal complex, characterized in that any one of Ti, Zr, Hf.
According to claim 2,
Any one of A, B, C is a chelated ligand containing a hetero atom or a hetero ring, and the hetero atom is any one of N, O and P. Metal complex, characterized in that.
delete According to claim 2,
When n is 3, the A and B are bonded to the central metal through a covalent bond or a coordinate bond, and the A and B are bonded to the central metal M together or individually.
delete According to claim 2,
A metal complex characterized by being represented by the following formula (7).

[Formula 7]

According to claim 2,
A metal complex characterized by being represented by the following formula (8) or formula (9).

[Formula 8]

[Formula 9]

A metal catalyst composition comprising the metal complex of claim 2.
A method for producing an ethylene/alpha-olefin/diene copolymer comprising contacting ethylene, an alpha-olefin having at least 4 carbon atoms, and a diene monomer with the metal catalyst composition of claim 10.
According to claim 11,
The alpha-olefin is
A method for preparing an ethylene/alpha-olefin/diene copolymer comprising at least one of 1-hexene and 1-octene.