KR20220104437A - Cobalt Complex Catalyst Containing Bispyrazolyl Ligand for Polymerization of Cyclic Olefin and Method for Preparing Cyclic Olefin Polymer Using the Same - Google Patents

Abstract

The present invention relates to a cobalt complex catalyst having a bispyrazolyl ligand for the polymerization of a cyclic olefin-based monomer and a preparation method of a cyclic olefin-based polymer using the same, and more particularly, to a cobalt complex catalyst having a bispyrazolyl ligand for the polymerization of a cyclic olefin-based monomer in which the cobalt complex catalyst having a bispyrazolyl ligand for the polymerization of cyclic olefin with high activity in the polymerization of a cyclic olefin-based monomer can be prepared and a cyclic olefin-based polymer can be prepared with high activity by polymerizing the cyclic olefin-based monomer in the presence of the cobalt complex catalyst having a bispyrazolyl ligand and a preparation method of a cyclic olefin-based polymer using the same.

Description

Cobalt Complex Catalyst Containing Bispyrazolyl Ligand for Polymerization of Cyclic Olefin and Method for Preparing Cyclic Olefin Polymer Using the Same

The present invention relates to a cobalt complex catalyst having a bispyrazolyl ligand for polymerization of a cyclic olefin monomer and a method for preparing a cyclic olefin polymer using the same, and more particularly, cobalt halide to a bispyrazolyl ligand as a catalyst for cyclic olefin polymerization. It relates to a method for preparing a cyclic olefin-based polymer by using a cobalt complex to which a compound is bound, and addition polymerization of a cyclic olefin-based monomer in the presence of the catalyst for polymerization of the cyclic olefin-based monomer.

Cyclic olefin-based polymers are polymers composed of cyclic olefin-based monomers such as norbornene. Compared to conventional olefin-based polymers, they have excellent transparency, heat resistance, and chemical resistance, and have very low birefringence and water absorption, so CD, DVD, POF (Plastic Optical Fiber) ), such as optical materials, capacitor films, information and electronic materials such as low dielectric materials, low-absorption syringes, and medical materials such as blister packaging.

In particular, norbornene polymer, as an amorphous polymer, has a high glass transition temperature, a high refractive index, and a low dielectric constant, so it is widely used as an electronic material, and many studies have been actively conducted by Heitz et al.

The catalyst used to polymerize the cyclic olefin-based polymer was mainly used as a catalyst complex including an organic phosphine compound as a cocatalyst as a sigma electron donor ligand. For example, in US Patent No. 6455650, [(R') _z M(L') _x (L'') _y ] _b [WCA] _d etc. are used as a catalyst complex, and as a ligand used here, A method of polymerizing a norbornene-based monomer using a hydrocarbon containing a hydrocarbyl group such as a phosphine compound and an allyl group is disclosed. In addition, in the literature by Lipian et al. (Non-Patent Document 0001), [(1,5-Cyclooctadiene)(CH ₃ )Pd(Cl)] is replaced with a phosphine such as PPh ₃ and [Na] ⁺ [B(3,5- (CF ₃ ) ₂ C ₆ H ₃ ) ₄ ] ^- A reaction of polymerization of norbornene by activation with a cocatalyst is disclosed.

However, when the phosphine cocatalyst is separately added, a separate step is required for the catalyst precursor to be converted into an active catalyst, and industrial usefulness is deteriorated due to excessive use of the expensive cocatalyst.

Meanwhile, in recent years, among various methods for improving the performance of a polymerization catalyst, it is possible to consider the electronic effect of the ligand while changing a part of the ligand to various functional groups. The improvement of catalyst performance according to such a change in the ligand electron effect can be found in several literatures. For example, it has been reported that the catalytic activity is improved by controlling the electron effect of the ligand while modifying the substituent of the Grubbs ruthenium carbine catalyst ligand (Non-Patent Documents 0002 and 0003).

Looking at the catalyst used for polymer synthesis, Waymouth discovered that the electron effect of the ligand plays a significant role in controlling the stereoselectivity of propylene polymerized using a zirconocene catalyst. (Non-patent document 0004). In addition, when the coat (Coates) copolymerizes carbon dioxide (CO ₂ ) and epoxide using a β-diiminate zinc alkoxide catalyst, a part of the ligand is cyano ) by changing the functional group to dramatically increase the polymerization rate of the polymer was announced (Non-Patent Document 0004).

However, there has been no report so far that a cobalt complex in which a cobalt halide compound is bonded to a bispyrazolyl ligand during polymerization of a cyclic olefin monomer has improved polymerization performance of a metal catalyst depending on the ligand.

(Patent Constitution 0001) US Registered Patent No. 5468819 (Announcement date: November 21, 1995) US Registered Patent No. 6455650 (published date: 2002.05.02)

Sen, et al., Organometallics 2001, Vol. 20, 2802-2812 Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29. Love, J. A.; Sanford, M. S.; Day, M. W.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 10103-10109. Lin, S.; Hauptman, E.; Lal, T. K.; Waymouth, R. M.; Quan, R. W.; Ernst, A. B. J. Mol. Catal. A: Chem. 1998, 136, 23-33. Moore, D. R.; Cheng, M.; Lobkovsky, E. B.; Coates, G. W. Angew. Chem., Int. Ed. 2002, 41, 2599-2602.

An object of the present invention is to provide a cobalt complex catalyst containing a bispyrazolyl ligand for cyclic olefin polymerization having high activity for polymerization of cyclic olefin monomers.

In addition, another object of the present invention is to provide a method for producing a cyclic olefin-based polymer capable of producing a cyclic olefin-based polymer with high activity by polymerizing a cyclic olefin-based monomer in the presence of the bispyrazolyl ligand-containing cobalt complex catalyst. .

In order to achieve the above object, one embodiment of the present invention provides a catalyst for polymerization of a cyclic olefin-based monomer, which is represented by the following formula (1) and is composed of a cobalt complex containing a bispyrazolyl ligand.

[Formula 1]

In Formula 1, R ₁ to R ₄ are the same or different, each independently a hydrogen atom or an alkyl group, L is -(CH ₂ ) _y - (where y is an integer of 0 to 5), and Q is the same or different, each independently a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; and a substituted or unsubstituted heteroaryl group, X ₁ and X ₂ are the same or different, each independently a halogen group, and a dotted line indicates the presence or absence of a bond.

In a preferred embodiment of the present invention, Q in Formula 1 is the same or different, and each independently a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms; a substituted or unsubstituted C 1 to C 5 alkyl group; a substituted or unsubstituted allyl group having 6 to 20 carbon atoms; And it is characterized in that it is selected from the group consisting of a heteroaryl group having 2 to 20 carbon atoms having O, N or S substituted or unsubstituted.

In a preferred embodiment of the present invention, X ₁ and X ₂ in Formula 1 are the same or different, each independently Cl or Br, and a dotted line indicates the presence or absence of a bond.

In a preferred embodiment of the present invention, R ₁ to R ₄ in Formula 1 may be the same or different, and each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In a preferred embodiment of the present invention, Chemical Formula 1 may be represented by the following Chemical Formulas 1a to 1g.

[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

[Formula 1g]

Another embodiment of the present invention provides a method for producing a cyclic olefin-based polymer comprising the step of addition polymerization of a cyclic olefin-based monomer in the presence of the catalyst for polymerization of the cyclic olefin-based monomer.

In another preferred embodiment of the present invention, the cyclic olefinic monomer is composed of norbornene, dicyclopentadiene, cyclopentadiene, cyclopentene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene and derivatives thereof. It may be characterized in that at least one selected from the group.

In another preferred embodiment of the present invention, the cyclic olefin-based monomer may be a compound represented by the following formula (2).

[Formula 2]

In Formula 2, m is an integer of 0 to 4, R ₅ to R ₈ are the same or different, and each independently a hydrogen atom; halogen atom; hydroxyl group; carboxyl group; a linear or branched alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms; an aryl group having 6 to 20 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; and an acyl group having 1 to 10 carbon atoms.

In another preferred embodiment of the present invention, the method for preparing the cyclic olefin-based polymer may be characterized in that the cyclic olefin-based monomer is addition-polymerized in the presence of a cocatalyst together with a catalyst for polymerization of the cyclic olefin-based monomer.

In another preferred embodiment of the present invention, the promoter is modified methylaluminoxane (MMAO), trimethyl aluminum (TMA), triethyl aluminum (TEA), triisobutyl aluminum (triiso- butyl aluminum (TIBAL), dimethyl chloro aluminum (DMCA), and diethyl chloroaluminum (DECA) may be characterized in that at least one selected from the group consisting of.

In another preferred embodiment of the present invention, the cocatalyst may be characterized in that modified methylaluminoxane (MMAO).

In another preferred embodiment of the present invention, the addition polymerization is 1,2-dichlorobenzene, toluene, n-pentane, n-hexane, n-heptane, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane and It may be characterized by polymerization in one or more solvents selected from the group consisting of 1,1,2,2-tetrachloroethane.

According to the present invention, it is possible to provide a cobalt complex catalyst having a bispyrazolyl ligand for cyclic olefin polymerization having high activity for polymerization of a cyclic olefin monomer, and in the presence of the cobalt complex catalyst having the bispyrazolyl ligand A cyclic olefin-based polymer can be prepared with high activity by polymerizing the olefin-based monomer.

1 is a view showing the X-ray structure of the cobalt complex catalyst of Preparation Example 3 according to the present invention.
2 is a view showing the X-ray structure of the cobalt complex catalyst of Preparation Example 5 according to the present invention.
3 is a view showing the X-ray structure of the cobalt complex catalyst of Preparation Example 6 according to the present invention.
4 is a view showing the X-ray structure of the cobalt complex catalyst of Preparation Example 7 according to the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is those well known and commonly used in the art.

Throughout this specification, when a part 'includes' a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

In one aspect, the present invention relates to a catalyst for polymerization of a cyclic olefin-based monomer, which is represented by the following formula (1) and comprises a cobalt complex containing a bispyrazolyl ligand.

[Formula 1]

In Formula 1, R ₁ to R ₄ are the same or different, each independently a hydrogen atom or an alkyl group, L is -(CH ₂ ) _y - (where y is an integer of 0 to 5), and Q is the same or different, each independently a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; and a substituted or unsubstituted heteroaryl group, X ₁ and X ₂ are the same or different, each independently a halogen group, and a dotted line indicates the presence or absence of a bond.

In R ₁ to R ₄ of Formula 1, the alkyl group represents a substituted or unsubstituted linear or branched methyl group, an ethyl group, a butyl group, and the like, and may contain 1 or more carbon atoms, preferably having 1 to carbon atoms. It may be an alkyl group of 10, more preferably an alkyl group of 1 to 3 carbon atoms.

In addition, in Q of Formula 1, the substituted or unsubstituted cycloalkyl group is a substituted or unsubstituted cyclopentyl group; a substituted or unsubstituted cyclohexyl group; As a substituent including a substituted or unsubstituted cycloheptyl group, it may have 3 or more carbon atoms, and preferably, the cycloalkyl group may have 3 to 10 carbon atoms.

In addition, in Q of Formula 1, the substituted or unsubstituted alkyl group is a substituted or unsubstituted methyl group; a substituted or unsubstituted ethyl group; Represents a substituted or unsubstituted butyl group and the like, and may contain 1 or more carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

In addition, in Q, a substituted or unsubstituted aryl group is an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, and is an allyl group having 6 to 20 carbon atoms, for example, a phenyl group, an o-biphenyl group, m-ratio Phenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, perylenyl group , chrysenyl, naphthacenyl, fluoranthenyl, and the like, and at least one hydrogen atom of the aryl group is a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group, a carboxyl group, a sulfonic acid group , may be substituted with a phosphoric acid group, an alkyl group having 1 to 10 carbon atoms, or the like.

In addition, in Q, a substituted or unsubstituted heteroaryl group includes 1, 2, or 3 heteroatoms selected from N, O and S, and the remaining ring atoms mean a ring aromatic system having 2 to 24 carbon atoms, and , It may be an aromatic heterocyclic compound having 2 to 20 carbon atoms, preferably substituted or unsubstituted, and having O, N, or S as a hetero atom.

In the present invention, 'substitution' in 'substituted or unsubstituted' means an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, and a heteroalkyl group having 1 to 24 carbon atoms. It means substituted with one or more substituents selected from the group consisting of an aryl group having 6 to 24 and an arylalkyl group having 7 to 24 carbon atoms.

In addition, considering the range of the alkyl group or aryl group in the 'C1-C12 alkyl group', 'C6-C24 allyl group', etc. in the present invention, the alkyl group having 1 to 12 carbon atoms and 6 to carbon atoms The carbon number range of the aryl group of 24 means the total number of carbon atoms constituting the alkyl portion or the aryl portion when viewed as unsubstituted without considering the portion substituted by the substituent.

In addition, in X ₁ and X ₂ of Formula 1, the halogen group may be at least one selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom (Cl) or a bromine atom (Br). have.

As a specific example, in Formula 1, R ₁ to R ₄ are the same or different, each independently a hydrogen atom or a methyl group, and L is -(CH ₂ ) _y - (where y is an integer of 0 or 1), and , Q are the same or different, and each independently a substituted or unsubstituted C5 to C8 cycloalkyl group, a substituted or unsubstituted C1 to C3 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, heterogeneous It is selected from the group consisting of a substituted or unsubstituted heteroaryl group having O as an atom, X ₁ and X ₂ are the same or different, each independently a chlorine atom, and the dotted line may be a bond or a non-bond.

More specifically, the complex catalyst represented by the following Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1a to 1g.

[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

[Formula 1g]

The complex catalyst represented by Formula 1 may be prepared by reacting an N,N-pyrazolylaniline derivative ligand represented by Formula 3 below with a cobalt halide precursor. In this case, the reaction of the N,N-pyrazolylaniline derivative ligand and the cobalt halide precursor may be at room temperature, preferably 10°C to 30°C, and the reaction time may be 10 hours to 48 hours.

[Formula 3]

In Formula 3, Q, L, and R ₁ to R ₄ are substantially the same as Q, L, and R ₁ to R ₄ described in Formula 1, and thus overlapping detailed descriptions will be omitted.

Specifically, the compound represented by Chemical Formula 3 may be a compound represented by the following Chemical Formulas 3a to 3g.

[Formula 3a]

[Formula 3b]

[Formula 3c]

[Formula 3d]

[Formula 3e]

[Formula 3f]

[Formula 3g]

In addition, the cobalt halide precursor may be cobalt chloride, cobalt bromide, cobalt iodine, etc., preferably cobalt chloride and cobalt bromide, and more preferably cobalt(II) chloride hexahydrate.

Such a catalyst preparation method can prepare a catalyst having good stability in air at a low cost and with a high yield.

In another aspect, the present invention relates to a method for producing a cyclic olefin-based polymer comprising the step of addition polymerization of a cyclic olefin-based monomer in the presence of the catalyst for polymerization of the aforementioned cyclic olefin-based monomer.

As the cyclic olefin-based monomer, any cyclic olefin monomer capable of forming a cyclic olefin-based polymer may be used. In the present invention, examples of the cyclic olefin monomer include norbornene (Nb) and its derivatives, dicyclopentadiene (DCPD) and its derivatives, cyclopentadiene (CPD) and its derivatives, and cyclopentene. , Cp) and its derivatives, cyclobutene (Cb) and its derivatives, cyclohexene (Chx) and its derivatives, cycloheptene (Chp) and its derivatives, cyclooctene (Cot) and its derivatives Any one or more selected from among may be used, and may preferably be a compound represented by the following formula (2).

[Formula 2]

In Formula 2, m is an integer of 0 to 4, R ₅ to R ₈ are the same or different, and each independently a hydrogen atom; halogen atom; hydroxyl group; carboxyl group; a linear or branched alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms; an aryl group having 6 to 20 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; and an acyl group having 1 to 10 carbon atoms.

In Formula 2, m is an integer of 0 to 2, R ₅ to R ₈ are the same or different, and each independently a hydrogen atom; carboxyl group; a linear or branched alkyl group having 1 to 5 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms; an aryl group having 6 to 18 carbon atoms; an alkoxy group having 1 to 5 carbon atoms; And it is preferable in terms of polymerization to be selected from the group consisting of an acyl group having 1 to 6 carbon atoms.

In the present invention, it is possible to homopolymerize the above-described cyclic olefin-based monomers, or copolymerize two or more cyclic olefin-based monomers, and also copolymerize the above-described cyclic olefin-based monomers with the olefin-based monomers. In this case, the olefin-based monomer can be used without limitation as long as it is an olefin-based monomer that can be addition-polymerized with the cyclic olefin-based monomer, and in terms of physical properties of the prepared polymer, vinyl acet, acrylate, alkyl methacrylate, methyl methacrylate, etc. It may be a monomer having the same polar vinyl group.

In the case of polymerizing the cyclic olefin-based monomer using the catalyst for polymerization of the cyclic olefin-based monomer of the present invention, the polymerization may be carried out in a slurry phase, liquid phase or gas phase. When the addition polymerization is carried out in a liquid phase or a slurry phase, a solvent or olefin itself may be used as a medium. The solvent used at this time is 1,2-dichlorobenzene, toluene, n-pentane, n-hexane, n-heptane, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane and 1,1,2,2- It may be at least one solvent selected from the group consisting of tetrachloroethane.

In addition, the polymerization may be carried out in a batch, semi-continuous or continuous manner, and the reaction conditions are 30 ° C. to 150 ° C. for 1 to 26 hours, when the reaction is performed at 30 ° C. or less than 1 hour. , there is a problem that the polymerization reaction does not proceed sufficiently, and when it is carried out at 150 ° C. or more than 26 hours, the polymer chain is decomposed to decrease the molecular weight or gelation may occur.

On the other hand, in the present invention, a cocatalyst may be additionally used for catalytic activity, and the cocatalyst used for polymerization is modified methylaluminoxane (MMAO), trimethyl aluminum (TMA), triethyl aluminum ( It may be at least one selected from the group consisting of triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL), dimethyl chloro aluminum (DMCA), and diethyl chloroaluminum (DECA). and preferably modified methylaluminoxane (MAO) in terms of catalytic activity.

As the modified methylaluminoxane, a known compound widely used in the prior art for catalytically polymerizing an olefinic copolymer may be used, and in the present invention, a known modified methylaluminoxane commercially available (manufactured by Tosoh) was used.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited by the following examples.

<Preparation Example 1: Preparation of cobalt complex C1>

1-1: Preparation of Ligand L1

Ligand L1 is described in S. Choi, S. Nayab, J. Jeon, SH Park, H. Lee, Inorg. Chim. With reference to Acta 438 (2015) 118 to 127, it was prepared in the following manner.

First, cyclohexanamine (2.28 mL, 0.02 mol) was dissolved in CH ₂ Cl ₂ (10.0 mL), and 1H-pyrazole-1-methanol (3.92 g, 0.04 mol) was dissolved in CH ₂ Cl ₂ (30.0 mL). and mixed. The mixture was reacted by stirring at room temperature for 72 hours. After completion of the reaction, MgSO ₄ was added to the reaction product, filtered through filter paper, and concentrated under reduced pressure to obtain ligand L1 (4.44 g, 85%) as a colorless oily liquid.

IR (liquid neat; cm ^-1 ): 3111 (w), 2928 (m), 2855 (w), 1510 (w), 1449 (w), 1387 (m), 1258 (m), 1130 (m), 1084 (m), 1042 (s), 966 (m), 882 (w), 745 (s), 653 (w), 614 (m).

1-2: Preparation of cobalt complex C1

Cobalt complex C1 is described in S. Choi, S. Nayab, J. Jeon, SH Park, H. Lee, Inorg. Chim. With reference to Acta 438 (2015) 118 to 127, it was prepared in the following manner.

Ligand L1 (0.259 g, 1.00 mmol) obtained in Preparation Example 1-1 was dissolved in absolute ethanol (10.0 mL), and then CoCl ₂ .6H ₂ O (0.237 g, 1.00 mmol) dissolved in absolute ethanol (10.0 mL) ) and stirred at room temperature for 12 hours to react. After completion of the reaction, the resulting blue solid powder was filtered, washed twice with cold ethanol (20.0 mL), and then washed three times with diethylether (20.0 mL). After washing, the product was dried in a vacuum oven to prepare cobalt complex C1 (0.31 g, 82 %).

IR (solid neat; cm ^-1 ): 3127 (w), 3111 (w), 2934 (w), 2859 (w), 1750 (w), 1518 (w), 1454 (m), 1402 (s), 1279 (s), 1196 (m), 1167 (m), 1117 (s), 1098 (m), 924 (w), 843 (w), 777 (s), 759 (s), 611 (s).

<Preparation Example 2: Preparation of cobalt complex C1>

2-1: Preparation of Ligand L2

Ligand L2 is described in S. Choi, S. Kim, H.-J. Lee, H. Lee, Inorg. Chem. Comm 44 (2014) 164-168 was prepared in the following manner.

First, cyclohexylmethanamine (2.26 g, 0.02 mol) was dissolved in CH ₂ Cl ₂ (30.0 mL), and 3,5dimethyl-1H-pyrazole-1-methanol (5.04 g, 0.04 mol) was added to CH ₂ Cl ₂ (30.0 mL). mL) and mixed. The mixture was stirred and reacted at room temperature for 72 hours, and after completion of the reaction, MgSO ₄ was added to the reaction product, filtered through filter paper, and then concentrated under reduced pressure to obtain ligand L2 (5.28 g, 80.2%) as a white solid. .

IR (solid neat; cm ^-1 ): 3265 (w), 2913 (s), 2846 (m), 1755 (m), 1693 (m), 1654 (m), 1550 (s), 1452 (s), 1421(s), 1379(s), 1317(s), 1246(s), 1180(s), 1145(m), 1106(s), 980(s), 855(w), 811(m), 771(s), 730(w).

2-2: Preparation of cobalt complex C2

Ligand L2 (0.329 g, 1.00 mmol) obtained in Preparation Example 2-1 was dissolved in absolute ethanol (10.0 mL), and then CoCl ₂ .6H ₂ O (0.237 g, 1.00 mmol) dissolved in absolute ethanol (10.0 mL). ) and stirred at room temperature for 12 hours to react. After completion of the reaction, the resulting blue solid powder was filtered, washed twice with cold ethanol (20.0 mL), and then washed three times with diethylether (20.0 mL). After washing, the product was dried in a vacuum oven to prepare cobalt complex C2 (0.36 g, 78 %).

IR (solid neat; cm ^-1 ): 3743 (m), 3617 (w), 3212 (w), 2919 (s), 2844 (m), 1838 (w), 1758 (w), 1694 (m), 1650 (m), 1549 (s), 1462 (s), 1305 (s), 1289 (m), 1225 (w), 1126 (m), 1039 (s), 981 (w), 855 (m), 789 (s), 627 (m).

<Preparation Example 3: Preparation of cobalt complex C3>

3-1: Ligand L3 Preparation

α-methylbenzylamine (3.00 mL, 23.2 mmol) was dissolved in CH ₂ Cl ₂ (50.0 mL), and 1H-pyrazole-1-methanol (4.55 g, 46.4 mmol) was dissolved in CH ₂ Cl ₂ (50.0 mL). and mixed. The mixture was stirred and reacted at room temperature for 72 hours. After completion of the reaction, MgSO ₄ was added to the reaction mass, filtered through filter paper, and concentrated under reduced pressure to obtain ligand L3 (5.00 g, 76%) as a colorless oil.

Analysis calculated for C ₁₆ H ₁₉ N ₅ (%): C, 68.30, H, 6.81, N, 24.89. Found: C, 68.25, H, 6.79, N, 24.50.

¹ H NMR (CDCl ₃ , 500 MHz): δ 7.56 (d, 2H, J = 1.22 Hz, -N-CH=CH-CH=N-), 7.44 (d, 2H, J = 2.29 Hz, -N- CH=CH-CH=N-), 7.34-7.27 (m, 5H, J = 34.18 Hz , -C ₆ H ₅ -), 6.29 (t, 2H, J = 4.12 Hz, -N-CH=CH-CH =N-), 5.12 (d, 2H, J = 13.73 Hz, N-CH ₂ -N), 4.99 (d, 2H, J = 13.89 Hz, -N-CH ₂ -N-), 4.12 (m, 1H) , J = 20.14 Hz, CH ₃ -CH-), 1.47 (d, 3H, J = 6.71 Hz, CH ₃ -CH-).

¹³ C NMR (CDCl ₃ , 125 MHz): δ 143.15 (s, 1C, C ₆ H ₅ -), 139.13 (d, 2C, J = 182.5 Hz, -N-CH=CH-CH=N-), 129.45 (d, 2C, J = 186.2 Hz , -N-CH=CH-CH=N-), 128.36 (s, 2C, C ₆ H ₅ -), 127.19 (s, 2C, C ₆ H ₅ -), 127.08 (s, 1C, C ₆ H ₅ -) 105.51 (d, 2C, J =178.02 Hz, -N-CH=CH-CH=N-), 64.36 (t, 2C, J = 303.3 Hz, -N-CH ₂ -N-), 57.80 (d, 1C, J = 137.1 Hz, CH ₃ -CH-), 19.22 (q, 1C , J = 385.1 Hz, CH ₃ -CH-).

FTIR (Colorless oily liquid neat; cm ^-1 ): 2974 (w), 1511 (w), 1448 (w), 1388 (m), 1282 (m), 1160 (m), 1084 (m), 1043 (m) ), 960 (w), 881 (w), 836 (w), 742 (s), 698 (s), 651 (w), 613 (m).

3-2: Preparation of cobalt complex C3

Ligand L3 (0.563 g, 2.00 mmol) obtained in Preparation Example 3-1 was dissolved in absolute ethanol (10.0 mL), and then CoCl ₂ .6H ₂ O (0.476 g, 2.00 mmol) dissolved in absolute ethanol (10.0 mL) ) and stirred at room temperature for 12 hours to react. After completion of the reaction, the resulting blue solid powder was filtered, washed twice with cold ethanol (20.0 mL), and then washed three times with diethylether (20.0 mL). After washing, the product was dried in a vacuum oven to prepare cobalt complex C3 (0.66 g, 80 %). The structure of the prepared cobalt complex C3 is shown in FIG. 1 .

Analysis calculated for C ₁₆ H ₁₉ Cl ₂ CoN ₅ (%): C, 46.73; H, 4.66, N; 17.03. Found: C, 46.88; H, 4.58; N, 17.34.

FTIR (solid neat; cm ^-1 ): 3753 (w), 3681 (w), 3114 (w), 2935 (w), 2371 (w), 1693 (w), 1514 (w), 1457 (w), 1403 (m), 1280 (m), 1211 (m), 1269 (w), 1133 (w), 1073 (m), 1003 (m), 951 (w), 906 (w), 830 (w), 765 (s), 704 (m), 641 (w), 608 (m).

<Preparation Example 4: Preparation of Cobalt Complex C4>

4-1: Ligand L4 Preparation

Ligand L4 is described in S. Choi, S. Nayab, J. Jeon, SH Park, H. Lee, Inorg. Chim. With reference to Acta 438 (2015) 118 to 127, it was prepared in the following manner.

First, (furan-2-yl)methanamine (1.77 mL, 2.00 mmol) was dissolved in CH ₂ Cl ₂ (10.0 mL), and 1H-pyrazole-1-methanol (3.92 g, 4.00 mmol) was added to CH ₂ Cl ₂ (30.0 mL) and mixed. The mixture was reacted by stirring at room temperature for 72 hours. After completion of the reaction, MgSO ₄ was added to the reaction product, filtered through filter paper, and then concentrated under reduced pressure to obtain ligand L4 (4.28 g, 83%) as a colorless oily liquid.

IR (liquid neat; cm ^-1 ): 3116 (w), 2949 (w), 1693 (w), 1510 (m), 1443 (w), 1384 (m), 1285 (m), 1139 (s), 1082(s), 1046(m), 1007(m), 962(m), 915(m), 870(w), 743(s), 609(s).

4-2: Preparation of cobalt complex C4

Cobalt complex C4 is described in S. Choi, S. Nayab, J. Jeon, SH Park, H. Lee, Inorg. Chim. With reference to Acta 438 (2015) 118 to 127, it was prepared in the following manner.

Ligand L4 (0.257 g, 1.00 mmol) obtained in Preparation Example 4-1 was dissolved in absolute ethanol (10.0 mL), and then CoCl ₂ .6H ₂ O (0.237 g, 1.00 mmol) dissolved in absolute ethanol (10.0 mL) ) and stirred at room temperature for 12 hours to react. After completion of the reaction, the resulting blue solid powder was filtered, washed twice with cold ethanol (20.0 mL), and then washed three times with diethylether (20.0 mL). After washing, the product was dried in a vacuum oven to prepare cobalt complex C4 (0.31 g, 82 %).

IR (solid neat; cm ^-1 ): 3824 (w), 3746 (w), 3126 (w), 1649 (w), 1511 (w), 1458 (w), 1396 (m), 1340 (w), 1277 (m), 1195 (w), 1107 (m), 1067 (m), 1016 (m), 988 (w), 845 (w), 764 (s), 645 (w), 605 (m).

<Preparation Example 5: Preparation of Cobalt Complex C5>

5-1: Preparation of Ligand L5

Ligand L5 is H. Cho., Synthesis and structure of Copper(II) complexes containing N'-Aromatic group substitited N,N',N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl) amines., Thesis for the degree of Master of Science, 2018, was prepared in the following manner with reference to Kyungpook National University.

First, 4-isopropylbenzenamine (3.00 mL, 22.0 mmol) was dissolved in CH ₂ Cl ₂ (50.0 mL), and 1H-pyrazole-1-methanol (4.31 g, 44.0 mmol) was added thereto CH ₂ Cl ₂ (50.0 mL) was dissolved and mixed. The mixture was reacted by stirring at room temperature for 72 hours. After completion of the reaction, MgSO ₄ was added to the reaction product, filtered through filter paper, and then concentrated under reduced pressure to obtain ligand L5 (5.00 g, 76%) as a colorless oily liquid.

IR (oily liquid neat; cm ^-1 ): 2958 (m), 2869 (m), 1614 (m), 1519 (s), 1460 (w), 1382 (m), 1348 (m), 1310 (m) , 1262(m), 1202(s), 1184(s), 1162(s), 1085(s), 1043(s), 956(m), 917(s), 821(m), 745(s) 651 (m), 612 (m).

5-2: Preparation of cobalt complex C5

Cobalt complex C5 (0.78 g, 92%) was prepared in the same manner as in Preparation Example 3-2 using the ligand L5 (0.591 g, 2.00 mmol) of Preparation Example 5-1 instead of the ligand L3 of Preparation Example 3-2. The structure of the prepared cobalt complex C5 is shown in FIG. 2 .

Analysis calculated for C ₁₇ H ₂₁ Cl ₂ CoN ₅ (%): C, 48.02; H, 4.98; N, 16.47. Found: C, 48.22; H, 5.00; N, 14.74.

FTIR (solid neat; cm ^-1 ): 3742 (w), 3685 (w), 2951 (w), 1611 (w), 1515 (m), 1456 (w), 1456 (m), 1402 (w), 1361 (m), 1311 (m), 1253 (m), 1188 (m), 1164 (s), 1101 (w), 1067 (s), 978 (w), 953 (w), 834 (w), 813(m), 790(m), 765(s), 745(s), 673(w), 641(m), 607(s), 578(m).

<Preparation Example 6: Preparation of Cobalt Complex C6>

6-1: Preparation of Ligand L6

Ligand L6 is described in F. Xue, J. Zhao, T. S. A. Hor, Dalton trans. 40 (2011) 8935 to 8940 were prepared in the following manner.

First, (furan-2-yl)methanamine (1.77 mL, 2.00 mmol) was dissolved in CH ₂ Cl ₂ (10.0 mL), and thereto 3,5dimethyl-1H-pyrazole-1-methanol (5.04 g, 0.04 mol) was dissolved in CH ₂ Cl ₂ (30.0 mL) and mixed. The mixture was reacted by stirring at room temperature for 72 hours. After completion of the reaction, MgSO ₄ was added to the reaction product, filtered through filter paper, and concentrated under reduced pressure to obtain ligand L6 (5.2 g, 82%) as a white solid.

¹ H-NMR (CDCl ₃ , 400 MHz): δ 7.34 (d, 1H, J = 2 Hz, -O-CH=CH-CH=C-), 6.30 (dd, 1H, J = 1.6 Hz, 2 Hz) , -O-CH=CH-CH=C-), 6.23 (d, 1H, J = 2.4 Hz, -O-CH=CH-CH=C-), 5.79 (s, 2H, -N=C(CH) ₃ )-CH=C(CH ₃ )-N-), 4.88 (s, 4H, -N-CH ₂ -N-), 3.76 (s, 2H, -O-CH=CH-CH=C-CH ₂ -N-), 2.19 (s, 6H, -N=C(CH ₃ )-CH=C(CH ₃ )-N-), 2.03 (s, 6H, -N=C(CH ₃ )-CH=C (CH ₃ )-N-).

6-2: Preparation of cobalt complex C6

Cobalt complex C5 (0.78 g, 88%) was prepared in the same manner as in Preparation Example 3-2 using the ligand L6 (0.627 g, 2.00 mmol) of Preparation Example 6-1 instead of the ligand L3 of Preparation Example 3-2. The structure of the prepared cobalt complex C6 is shown in FIG. 3 .

Analysis calculated for C ₁₇ H ₂₃ Cl ₂ N ₅ OCo: C, 46.07%, H, 5.23%, N, 15.80%. Found: C, 46.30%, H, 5.29%, N, 15.80%.

IR (solid neat; cm ^-1 ): 2921 (w), 2319 (w), 1546 (m), 1494 (w), 1463 (m), 1427 (w), 1383 (m), 1324 (w), 1286 (w), 1248 (w), 1151 (m), 1107 (m), 1042 (m), 1009 (m), 980 (m), 915 (w), 884 (m), 834 (w), 798 (s), 752 (s), 692 (w), 631 (w), 599 (w).

<Preparation Example 7: Preparation of Cobalt Complex C7>

7-1: Preparation of Ligand L7

Ligand L7 was prepared in the following manner with reference to H. Cho, S. Choe, D. Kim, H. Lee, S. Nayab, Polyhedron , 187 (2020) 114641 to 114650.

First, 4-isopropylaniline (3.00 ml, 0.02 mol) was dissolved in CH ₂ Cl ₂ (50.0 mL), and 3,5dimethyl-1H-pyrazole-1-methanol (5.04 g, 0.04 mol) was added thereto CH ₂ Cl ₂ (30.0 mL) and mixed. The mixture was reacted by stirring at room temperature for 72 hours. After completion of the reaction, MgSO ₄ was added to the reaction product, filtered through filter paper, and concentrated under reduced pressure to obtain ligand L7 (6.00 g, 76 %) as a yellow oil.

¹ H NMR (CDCl ₃ , 500 MHz): δ 7.09 (d, 2H, J = 8.39 Hz, -C ₆ H ₄ -), 6.95 (d, 2H, J = 8.70 Hz, -C ₆ H ₄ -), 5.73 (s, 2H, -NC(CH ₃ ))=CH-C(CH ₃ )=N-), 5.46 (s, 4H, -N-CH ₂ -N-), 2.85-2.80 (m, 1H, J = 27.62 Hz, iso-C ₃ H ₇ -), 2.20 (s, 6H, -NC(CH ₃ ))=CH-C(CH ₃ )=N-), 2.01 (s, 6H, -NC (CH) ₃ ))=CH-C(CH ₃ )=N-), 1.20 (d, 6H, J = 6.87 Hz iso-C ₃ H ₇ ).

7-2: Preparation of cobalt complex C7

Cobalt complex C7 (0.896 g, 92%) was prepared in the same manner as in Preparation Example 3-2 by using the ligand L7 (0.703 g, 2.00 mmol) of Preparation Example 7-1 instead of the ligand L3 of Preparation Example 3-2. The structure of the prepared cobalt complex C7 is shown in FIG. 4 .

Analysis calculated for C ₂₁ H ₂₉ Cl ₂ N ₅ Co: C, 52.40%, H, 6.07%, N, 14.55%. Found: C, 52.61%, H, 6.06%, N, 14.24%.

IR (solid neat; cm _-1 ): 2952 (w), 2921 (w), 1608 (w), 1551 (m), 1512 (m), 1460 (m), 1414 (m), 1376 (m), 1268 (s), 1210 (m), 1159 (m), 1122 (m), 1045 (s), 984 (w), 958 (w), 930 (s), 831 (s), 808 (m), 788(s), 701(s), 635(m), 570(s).

<Example 1: Preparation of norbornene (NB) polymer>

Norbornene was polymerized using the cobalt complex (C1) of Preparation Example 1 and the cobalt complex (C3) of Preparation Example 3 as catalysts, respectively.

First, the cobalt complex catalyst (15 μmol) was added to a Schlenk flask under argon and vacuum atmosphere, and then 5 ml of toluene (scavenger: MMAO) was added to dissolve the cobalt complex catalyst. 3.1 ml of modified methylaluminoxane (MMAO) was injected thereto, and then stirred in a 90° C. bath for 30 minutes. In another Schlenk flask under the same atmosphere, 1.422 g of norbornene was added, and 0.2 ml of tetralin and 15 ml of toluene were added to dissolve it, and then the activated cobalt complex catalyst was injected and the reaction was performed by stirring in a 90°C bath overnight. did. Then, methanol (2 mL + 2 mL Ar) was injected to terminate the reaction, and the reaction polymer was added to a solution in which methanol (500 mL) and HCl (5 mL) were added, followed by stirring for at least 30 minutes, and vacuum The final polymer was prepared by drying under reduced pressure.

At this time, the results of the polymerization were measured using NMR, and in the case of the cobalt complex catalyst (C1) of Preparation Example 1, it was found that the conversion rate was 51% and the yield was 87% (1.2315 g), and the cobalt of Preparation Example 3 was In the case of the complex catalyst (C3), it was found that the conversion rate was 60% and the yield was 86% (1.22 g).

<Example 2: Preparation of butylnorbornene (BuNB) polymer>

Butylnorbornene was polymerized using the cobalt complex (C1) of Preparation Example 1 as a catalyst.

First, the cobalt complex catalyst (15 μmol) was added to a Schlenk flask under argon and vacuum atmosphere, and then 5 ml of toluene (scavenger: MMAO) was added to dissolve the cobalt complex catalyst. 3.1 ml of modified methylaluminoxane (MMAO) was injected thereto, and then stirred in a 90°C bath for 30 minutes. 2.5 ml of butylnorbornene (BuNB) was added to another Schlenk flask in the same atmosphere, 0.2 ml of tetralin and 15 ml of toluene were added to dissolve, and then the activated cobalt complex catalyst was injected and stirred overnight in a 90°C bath. to carry out the reaction. Then, hexane (2 mL + 2 mL Ar) was injected to terminate the reaction, and the reaction polymer was added to a solution in which hexane (500 mL) and HCl (5 mL) were added, followed by stirring for at least 30 minutes, , and dried under vacuum to prepare a final polymer.

The results of the polymerization were measured using NMR, and in the case of the cobalt complex catalyst (C1) of Preparation Example 1, it was found that the yield was 32% (0.7008 g/2.22 g), and the conversion rate was the standard on NMR. The peaks were not integrated and thus could not be measured.

<Example 3: Preparation of methylnorbornene (MeNB) polymer>

Polymerization of methylnorbornene using the cobalt complex of Preparation Example 1 (C1), the cobalt complex of Preparation Example 3 (C3), the cobalt complex of Preparation Example 4 (C4), and the cobalt complex of Preparation Example 5 (C5) as catalysts, respectively did.

First, the cobalt complex catalyst (15 μmol) was added to a Schlenk flask under argon and vacuum atmosphere, and then 5 ml of toluene (scavenger: MMAO) was added to dissolve the cobalt complex catalyst. 3.1 ml of modified methylaluminoxane (MMAO) was injected thereto, and then stirred in a 90°C bath for 30 minutes. 2.2 ml of methylnorbornene (MeNB) was added to another Schlenk flask under the same atmosphere, 0.2 ml of tetralin and 15 ml of toluene were added to dissolve, and the activated cobalt complex catalyst was injected and stirred overnight in a 90°C bath. to carry out the reaction. Then, hexane (2 mL + 2 mL Ar) was injected to terminate the reaction, and the reaction polymer was added to a solution in which hexane (Hex) (500 mL) and HCl (5 mL) were added, followed by stirring for at least 30 minutes. and dried under vacuum to prepare a final polymer.

At this time, the results of the polymerization were measured using NMR, and in the case of the cobalt complex catalyst (C1) of Preparation Example 1, it was found that the conversion rate was 52% and the yield was 25% (0.5732 g), and the cobalt of Preparation Example 3 was In the case of the complex catalyst (C3), it was found that the conversion rate was 42% and the yield was 19%. In addition, in the case of the cobalt complex catalyst (C4) of Preparation Example 4, the conversion rate was 19% and the yield was 4%, and in the case of the cobalt complex catalyst (C5) of Preparation Example 5, the conversion rate was 16% and the yield was 3.5%. appear.

<Example 4: Preparation of a copolymer of norbornene (NB) and methyl methacrylate (MMA)>

Norbornene and methyl methacrylate were copolymerized using the cobalt complex (C1) of Preparation Example 1 and the cobalt complex (C3) of Preparation Example 3 as catalysts, respectively.

First, the cobalt complex catalyst (15 μmol) was added to a Schlenk flask under argon and vacuum atmosphere, and then 5 ml of toluene (scavenger: MMAO) was added to dissolve the cobalt complex catalyst. 3.1 ml of modified methylaluminoxane (MMAO) was injected thereto, and then stirred in a 90°C bath for 30 minutes. In another Schlenk flask under the same atmosphere, 2.1890 g of norbornene (NB) was added, and 2.5 ml of methyl methacrylate (MMA), 0.63 ml of tetralin, and 15 ml of toluene were added and dissolved, followed by dissolution of the activated cobalt complex. The reaction was carried out by injecting the catalyst and stirring it overnight in a 90 °C bath. Then, methanol (2 mL + 2 mL Ar) was injected to terminate the reaction, and the reaction polymer was added to a solution in which methanol (500 mL) and HCl (5 mL) were added, followed by stirring for at least 30 minutes, and vacuum The final copolymer was prepared by drying under reduced pressure.

At this time, the results of the polymerization were measured using NMR, and in the case of the cobalt complex catalyst (C1) of Preparation Example 1, the MMA conversion rate was 60%, the NB conversion rate was 37%, and the yield was 11% (0.5021 g). , in the case of the cobalt complex catalyst (C3) of Preparation Example 3, the MMA conversion rate was 59%, the NB conversion rate was 60%, and the yield was 13% (0.6029 g).

<Example 5: Preparation of dicyclopentadiene (DCPD) polymer>

Dicyclopentadiene (DCPD) was polymerized using the cobalt complex (C1) of Preparation Example 1 as a catalyst.

First, the cobalt complex catalyst (15 μmol) was added to a Schlenk flask under argon and vacuum atmosphere, and then 5 ml of toluene (scavenger: MMAO) was added to dissolve the cobalt complex catalyst. 3.1 ml of modified methylaluminoxane (MMAO) was injected thereto, and then stirred in a 60°C bath for 30 minutes. 2 ml of dicyclopentadiene (DCPD) was added to another Schlenk flask in the same atmosphere, 0.2 ml of tetralin and 15 ml of toluene were added to dissolve it, and then the activated cobalt complex catalyst was injected in a bath at 60° C. for 2 hours. The reaction was carried out by stirring for a while. Then, hexane (2 mL + 2 mL Ar) was injected to terminate the reaction, and the reaction polymer was added to a solution in which hexane (500 mL) and HCl (5 mL) were added, followed by stirring for at least 30 minutes, , and dried under vacuum to prepare a final polymer.

The results of the polymerization were measured using NMR, and in the case of the cobalt complex catalyst (C1) of Preparation Example 1, it was found that the yield was 3.5% (1.972 g), and the conversion rate was the peaks as a reference on NMR. Measurement was not possible due to lack of integration.

<Example 6: Preparation of a copolymer of dicyclopentadiene (DCPD) and methyl methacrylate (MMA)>

Dicyclopentadiene (DCPD) and methyl methacrylate (MMA) were copolymerized using the cobalt complex (C1) of Preparation Example 1 as a catalyst.

First, the cobalt complex catalyst (15 μmol) was added to a Schlenk flask under argon and vacuum atmosphere, and then 5 ml of toluene (scavenger: MMAO) was added to dissolve the cobalt complex catalyst. 3.1 ml of modified methylaluminoxane (MMAO) was injected thereto, and then stirred in a 60°C bath for 30 minutes. In another Schlenk flask under the same atmosphere, 3.1 ml of dicyclopentadiene (DCPD) and 2.5 ml of methyl methacrylate (MMA) were added, and 0.63 ml of tetralin and 15 ml of toluene were added to dissolve it, and then the activated A cobalt complex catalyst was injected, and the reaction was performed by stirring in a bath at 60° C. for 2 hours. Then, hexane (2 mL + 2 mL Ar) was injected to terminate the reaction, and the reaction polymer was added to a solution in which hexane (500 mL) and HCl (5 mL) were added, followed by stirring for at least 30 minutes, , and vacuum drying to prepare a final copolymer (0.1860 g).

At this time, the results of the polymerization were measured using NMR, and in the case of the cobalt complex catalyst (C1) of Preparation Example 1, the MMA conversion rate was 9%, and it was found that the Tg of the copolymer was 256.73 ° C.

Therefore, according to the present invention, it is possible to provide a cobalt complex catalyst having a bispyrazolyl ligand for cyclic olefin polymerization having high activity for polymerization of a cyclic olefin monomer, and in the presence of the cobalt complex catalyst having the bispyrazolyl ligand It was confirmed that the cyclic olefin-based polymer can be prepared with high activity by polymerizing the cyclic olefin-based monomer.

The present invention is not limited by the above-described embodiments and the accompanying drawings, and it is common in the art to which the present invention pertains that various substitutions, modifications, and changes are possible within the scope of the technical spirit of the present invention. It will be clear to those who have knowledge.

Claims (14)

Catalyst for polymerization of cyclic olefin monomers, characterized in that it is represented by the following formula (1) and consists of a cobalt complex containing a bispyrazolyl ligand:
[Formula 1]

In Formula 1,
R ₁ to R ₄ are the same or different, and each independently represents a hydrogen atom or an alkyl group,
L is -(CH ₂ ) _y -, where y is an integer from 0 to 5,
Q is the same or different, each independently a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; And selected from the group consisting of a substituted or unsubstituted heteroaryl group,
X ₁ and X ₂ are the same or different, each independently a halogen group, and a dotted line indicates the presence or absence of a bond.
According to claim 1,
Q in Formula 1 is the same or different, and each independently a substituted or unsubstituted C3-10 cycloalkyl group; a substituted or unsubstituted C 1 to C 5 alkyl group; a substituted or unsubstituted allyl group having 6 to 20 carbon atoms; and a substituent selected from the group consisting of a C 2 to C 20 heteroaryl group having substituted or unsubstituted O, N or S. Catalyst for polymerization of a cyclic olefin-based monomer.
According to claim 1,
X ₁ and X ₂ of Formula 1 are the same or different, and each independently Cl or Br. A catalyst for polymerization of a cyclic olefin-based monomer.
According to claim 1,
R ₁ to R ₄ in Formula 1 are the same or different, and each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
According to claim 1,
The formula 1 is a catalyst for polymerization of a cyclic olefin monomer, characterized in that represented by the formula 1a or 1b below:
[Formula 1a]

[Formula 1b]

According to claim 1,
Chemical Formula 1 is a catalyst for polymerization of cyclic olefin-based monomers, characterized in that it is represented by any one of the following Chemical Formulas 1c to 1e:
[Formula 1c]

[Formula 1d]

[Formula 1e]

According to claim 1,
The formula 1 is a catalyst for polymerization of a cyclic olefin-based monomer, characterized in that represented by the formula 1f or 1g below:
[Formula 1f]

[Formula 1g]

A method for producing a cyclic olefin-based polymer, comprising the step of addition polymerization of a cyclic olefin-based monomer in the presence of the catalyst for polymerization of any one of claims 1 to 7.
9. The method of claim 8,
The cyclic olefin monomer is at least one selected from the group consisting of norbornene, dicyclopentadiene, cyclopentadiene, cyclopentene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and derivatives thereof. A method for producing a cyclic olefin-based polymer comprising:
9. The method of claim 8,
The method for producing a cyclic olefin-based polymer, characterized in that the cyclic olefin-based monomer is a compound represented by the following formula 2:
[Formula 2]

In Formula 2,
m is an integer from 0 to 4,
R ₅ to R ₈ are the same or different, and each independently a hydrogen atom; halogen atom; hydroxyl group; carboxyl group; a linear or branched alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms; an aryl group having 6 to 20 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; and an acyl group having 1 to 10 carbon atoms.
9. The method of claim 8,
The method for producing the cyclic olefin-based polymer is a method for producing a cyclic olefin-based polymer, characterized in that the addition polymerization of the cyclic olefin-based monomer in the presence of a cocatalyst together with a catalyst for polymerization of the cyclic olefin-based monomer.
12. The method of claim 11,
The promoter is modified methylaluminoxane (MMAO), trimethyl aluminum (TMA), triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL), dimethylchloro aluminum (dimethyl chloro aluminum, DMCA) and diethyl chloro aluminum (diethyl chloroaluminum, DECA) method for producing a cyclic olefin-based polymer, characterized in that at least one selected from the group consisting of.
12. The method of claim 11,
The method for producing a cyclic olefin-based polymer, characterized in that the cocatalyst is modified methylaluminoxane (MMAO).
9. The method of claim 8,
The addition polymerization is 1,2-dichlorobenzene, toluene, n-pentane, n-hexane, n-heptane, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane and 1,1,2,2-tetra A method for producing a cyclic olefin-based polymer, characterized in that polymerization in one or more solvents selected from the group consisting of chloroethane.

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