KR102486898B1 - Cobalt Complex Catalyst Containing Imine 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 containing an imine ligand for polymerization of a cyclic olefin monomer and a method for preparing a cyclic olefin polymer using the same, and more particularly, to a catalyst having an imine ligand having high activity in polymerization of a cyclic olefin monomer. Contains an imine ligand for polymerization of a cyclic olefin monomer capable of providing a cobalt complex catalyst and producing a cyclic olefin polymer with high activity by polymerizing a cyclic olefin monomer in the presence of a cobalt complex catalyst having the above imine ligand. It relates to a cobalt complex catalyst and a method for preparing a cyclic olefin-based polymer using the same.

Description

Cobalt Complex Catalyst Containing Imine 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 containing an imine-based ligand for polymerization of cyclic olefin-based monomers and a method for preparing a cyclic olefin-based polymer using the same, and more particularly, to a catalyst for cyclic olefin-based polymerization in which a halogenated cobalt compound is bonded to an imine-based ligand. It relates to a method for preparing a cyclic olefin-based polymer by addition polymerization of a cyclic olefin-based monomer in the presence of the above catalyst for polymerization of a cyclic olefin-based monomer using a complex formed thereon.

Cyclic olefin-based polymer is a polymer composed of cyclic olefin-based monomers such as norbornene, and has excellent transparency, heat resistance, and chemical resistance compared to conventional olefin-based polymers, and has very low birefringence and water absorption, resulting in CD, DVD, and POF (Plastic Optical Fibers). ), such as optical materials, capacitor films, information and electronic materials such as low-dielectric materials, low-absorbent syringes, and medical materials such as blister packaging.

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

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

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

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

Looking at catalysts used in polymer synthesis, Waymouth discovered that the electronic effect of a ligand plays an important role in controlling the stereoselectivity of propylene polymerized using a zirconocene catalyst. (Non-Patent Document 0004). In addition, when 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, the polymer polymerization rate was dramatically increased (Non-Patent Document 0004).

However, no case has been reported so far in which the polymerization performance of a metal catalyst according to a ligand is improved by using a complex in which a halogenated cobalt compound is bonded to an imine ligand during polymerization of a cyclic olefin monomer.

(Patent Division 0001) US Patent No. 5468819 (Announcement date: 1995.11.21) US Patent Registration No. 6455650 (Publication 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 an imine ligand for polymerization of cyclic olefin monomers having high activity in polymerization of cyclic olefin monomers.

In addition, another object of the present invention is to provide a method for preparing 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 above imine-based ligand-containing cobalt complex catalyst.

In order to achieve the above object, one embodiment of the present invention is an imine-based ligand for polymerization of a cyclic olefin monomer, characterized in that it comprises at least one of a compound represented by the following formula (1) and a compound represented by the following formula (2) A containing cobalt complex catalyst is provided.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, R ₁ to R ₄ are the same or different, and each independently a hydrogen atom; It is selected from the group consisting of a substituted or unsubstituted alkyl group, X ₁ to X ₄ are the same or different, each independently a halogen group, and L is -(CH ₂ ) _y - (where y is an integer from 1 to 5) ), Z is an oxygen atom, a nitrogen atom, a carbon atom, and is selected from the group consisting of -(CH ₂ )-, n is an integer of 0 or 1, m is an integer of 0 to 3, and the dotted line indicates the presence of a bond. or indicate absence.

In a preferred embodiment of the present invention, X ₁ to X ₄ in Chemical Formulas 1 and 2 may be the same or different, and may each independently represent Cl or Br.

In a preferred embodiment of the present invention, R ₁ to R ₄ in Formulas 1 and 2 are the same or different, and each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. .

In a preferred embodiment of the present invention, the compound represented by Formula 1 may be characterized by being represented by any one of Formulas 1a to 1c below.

[Formula 1a]

[Formula 1b]

[Formula 1c]

In a preferred embodiment of the present invention, the compound represented by Formula 2 may be characterized in that it is represented by Formula 2a below.

[Formula 2a]

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 a cobalt complex catalyst containing an imine ligand for polymerization of the cyclic olefin-based monomer. .

In another preferred embodiment of the present invention, the cyclic olefin monomer is selected from the group consisting of norbornene, dicyclopentadiene, cyclopentadiene, cyclopentene, cyclobutene, cyclohexene, cycloheptene, cyclooctene, and derivatives thereof. It may be characterized in that one or more species are.

In another preferred embodiment of the present invention, the cyclic olefin monomer may be a compound represented by Formula 3 below.

[Formula 3]

In Formula 3, n is an integer of 0 to 4, R ₁₁ to R ₁₄ are the same or different, and each independently a hydrogen atom; halogen atom; hydroxy 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 producing the cyclic olefin-based polymer is characterized in that addition polymerization of the cyclic olefin-based monomer is carried out in the presence of a cocatalyst together with a complex cobalt catalyst containing an imine ligand for polymerization of the cyclic olefin-based monomer. can

In another preferred embodiment of the present invention, the cocatalyst is modified methylaluminoxane (MMAO), trimethyl aluminum (TMA), triethyl aluminum (TEA), triisobutyl aluminum (triiso- butyl aluminum, TIBAL), dimethyl chloro aluminum (DMCA), and diethyl chloroaluminum (DECA).

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 in that it is polymerized 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 an imine ligand for cyclic olefin polymerization having high activity in polymerization of cyclic olefin monomers, in the presence of a cobalt complex catalyst having the above imine ligand. A cyclic olefin-based polymer with high activity can be prepared by polymerizing the monomers.

1 is a view showing the X-ray structure of the cobalt complex catalyst of Preparation Example 1 according to the present invention.
2 is a view showing the X-ray structure of the cobalt complex catalyst of Preparation Example 2 according to the present invention.
3 is a view showing the X-ray structure of the cobalt complex catalyst of Preparation Example 4 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 nomenclatures used herein are those well known and commonly used in the art.

Throughout the present specification, when a part 'includes' a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

In one aspect, the present invention relates to a cobalt complex catalyst containing an imine ligand for polymerization of a cyclic olefin-based monomer comprising at least one of a compound represented by Formula 1 below and a compound represented by Formula 2 below.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, R ₁ to R ₄ are the same or different, and each independently a hydrogen atom; It is selected from the group consisting of a substituted or unsubstituted alkyl group, X ₁ to X ₄ are the same or different, each independently a halogen group, and L is -(CH ₂ ) _y - (where y is an integer from 1 to 5) ), Z is an oxygen atom, a nitrogen atom, a carbon atom, and is selected from the group consisting of -(CH ₂ )-, n is an integer of 0 or 1, m is an integer of 0 to 3, and the dotted line indicates the presence of a bond. or indicate absence.

In R ₁ to R ₄ of Formulas 1 and 2, the alkyl group represents a substituted or unsubstituted linear or branched methyl group, ethyl group, propyl group, butyl group, hexyl group, etc., and may contain 1 or more carbon atoms. It may be preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

In the present invention, 'substitution' in 'substituted or unsubstituted' refers to an alkyl group having 1 to 10 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 carbon atom group. It means substituted with one or more substituents selected from the group consisting of an aryl group having 6 to 24 carbon atoms and an arylalkyl group having 7 to 24 carbon atoms.

In addition, considering the range of the alkyl group or aryl group in the 'alkyl group having 1 to 10 carbon atoms', the 'allyl group having 6 to 24 carbon atoms', etc. in the present invention, the alkyl group having 1 to 10 carbon atoms and the carbon number 6 to 24 The carbon number range of the aryl group of means the total number of carbon atoms constituting the alkyl part or the aryl part when regarded as unsubstituted without considering the part where the substituent is substituted.

Meanwhile, in X ₁ and X ₄ of Chemical Formulas 1 and 2, the halogen group may be at least one selected from the group consisting of chlorine atoms (Cl), bromine atoms (Br), and iodine atoms (I), preferably chlorine. It may be an atom (Cl) or a bromine atom (Br), m in Chemical Formulas 1 and 2 is an integer of 0 to 3, preferably m may be an integer of 0 to 2.

Specifically, in Formulas 1 and 2, R ₁ to R ₄ are the same or different, and each independently a hydrogen atom; It is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, X ₁ to X ₄ are chlorine atoms, L is -(CH ₂ )y- (here, y is an integer of 1 to 5), Z is an oxygen atom, a nitrogen atom, and is selected from the group consisting of -(CH ₂ )-, n is an integer of 0 or 1, m is an integer of 0 to 3, and a dotted line may indicate the presence or absence of a bond. there is.

More specifically, the cobalt complex catalyst for polymerization of cyclic olefin monomers according to an embodiment of the present invention includes a complex catalyst in which an iminopyridine ligand and a halogenated cobalt compound are combined and a complex catalyst in which an iminoquinolyl ligand and a halogenated cobalt compound are bonded. , It may include at least one of the compounds represented by Chemical Formulas 1a to 1c and Chemical Formula 2a.

[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 2a]

The cobalt complex catalyst represented by Chemical Formula 1 may be prepared by reacting an imine-based derivative ligand represented by Chemical Formula 4 with a cobalt halide precursor. At this time, the reaction between the imine-based derivative ligand and the cobalt halide precursor may be room temperature (room temperature), preferably 10 °C to 30 °C, and the reaction time may be 10 hours to 48 hours.

[Formula 4]

In Formula 4, R ₁ , R ₂ , Z, L, n, and m are substantially the same as R ₁ , R ₂ , Z, L, n, and m described in Formula 1, and thus overlapping detailed descriptions are omitted.

Specifically, the compound represented by Chemical Formula 4 may be, for example, a compound represented by any one of Chemical Formulas 4a to 4f below.

[Formula 4a]

[Formula 4b]

[Formula 4c]

In addition, the cobalt complex catalyst represented by Chemical Formula 2 may be prepared by reacting an imine-based derivative ligand represented by Chemical Formula 5 with a cobalt halide precursor. At this time, the reaction between the imine-based derivative ligand and the cobalt halide precursor may be room temperature, preferably 10 °C to 30 °C, and the reaction time may be 10 hours to 48 hours.

[Formula 5]

In Formula 5, R ₃ and R ₄ are substantially the same as R ₃ and R ₄ described in Formula 2, and thus overlapping detailed descriptions are omitted.

Specifically, the compound represented by Formula 5 may be, for example, a compound represented by Formula 5a below.

[Formula 5a]

The cobalt halide precursor may be cobalt chloride, cobalt bromo, cobalt iodo, etc., preferably cobalt chloride and cobalt bromine, more preferably cobalt(II) chloride hexahydrate.

Such a method for preparing a catalyst can produce a catalyst with good stability in air at low cost and high yield.

From another point of view, 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 a cobalt complex catalyst containing an imine ligand for polymerization of the above-described cyclic olefin-based monomer. .

As the cyclic olefin monomer, any cyclic olefin monomer capable of forming a cyclic olefin polymer may be used. Examples of such cyclic olefin monomers in the present invention include norbornene (Nb) and its derivatives, dicyclopentadiene (DCPD) and its derivatives, cyclopentadiene (CPD) and its derivatives, and cyclopentene (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 may be used, and preferably may be a compound represented by the following formula (3).

[Formula 3]

In Formula 3, n is an integer of 0 to 4, R ₁₁ to R ₁₄ are the same or different, and each independently a hydrogen atom; halogen atom; hydroxy 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 3, n is an integer of 0 to 2, R ₁₁ to R ₁₄ 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 preferably selected from the group consisting of an acyl group having 1 to 6 carbon atoms in terms of polymerization.

In the present invention, the above cyclic olefin monomers may be homopolymerized, two or more cyclic olefin monomers may be copolymerized, or the above cyclic olefin monomers and olefin monomers may be copolymerized. At this time, the olefin-based monomer can be used without limitation as long as it is an olefin-based monomer capable of addition polymerization with the cyclic olefin-based monomer, and in terms of the physical properties of the prepared polymer, vinylacet, acrylate, alkyl methacrylate, methyl methacrylate, etc. It may be a monomer having the same polar vinyl group.

When the cyclic olefin-based monomer is polymerized 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, a liquid phase, or a gas phase. When addition polymerization is carried out in a liquid or slurry phase, a solvent or olefin itself can 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 one or more solvents 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. , A problem occurs that the polymerization reaction does not sufficiently proceed, and when carried out at 150 ° C. or over 26 hours, the polymer chain may be decomposed and the molecular weight may decrease or gelation may occur.

Meanwhile, in the present invention, a cocatalyst may be additionally used for catalytic activity, and cocatalysts used for polymerization include modified methylaluminoxane (MMAO), trimethyl aluminum (TMA), and triethyl aluminum ( It may be one or more selected from the group consisting of triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL), dimethyl chloro aluminum (DMCA), and diethyl chloroaluminum (DECA) And, in terms of catalytic activity, it may be preferably modified methylaluminoxane (MAO).

As the modified methylaluminoxane, known compounds widely used in the prior art of catalytically polymerizing cyclic olefin-based polymers may be used, and known modified methylaluminoxane commercially available in the present invention was also used.

Hereinafter, the present invention will be specifically described 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

2-Quinolinecarboxaldehyde (0.600 g, 3.8 mmol) was dissolved in CH ₂ Cl ₂ (10.0 mL), and a solution of 3-methoxypropylamine (0.338 g, 3.8 mmol) dissolved in CH ₂ Cl ₂ (10.0 mL) was mixed. did The mixture was refluxed at 40 °C and reacted by stirring for 48 hours. After completion of the reaction, MgSO ₄ was added to the reactant, filtered through filter paper, and concentrated under reduced pressure to obtain ligand L1 (0.7973 g, 81%) as dark red oil represented by Chemical Formula 4a.

¹ H NMR (CDCl ₃ , 500 MHz): δ 8.55 (s, 1H, -CH ₂ -CH=NC-) 8.15 (t, 1H, J = 8.34 Hz, -CH-CH=C-), 8.13 (t , 1H, J = 10.72 Hz, -CH-CH=C-), 8.11 (d, 1H, J = 8.58 Hz, -CH-CH=C-), 7.81 (d, 1H, J = 8.34 Hz, -CH -CH=CH-), 7.71 (t, 1H, J = 7.64 Hz, -CH-CH=CH-), 7.54 (t, 1H, J = 7.52 Hz, -CH-CH=CH-), 3.76(t , 2H, J = 7.01 Hz, -O-CH ₂ -CH ₂ -), 2.41(t, 2H, J = 7.98 Hz, -CH ₂ -CH ₂ -N=), 2.26(s, 3H, -O- CH ₃ ), 1.94 (m, 2H, J = 7.27 Hz, -CH ₂ -CH ₂ -CH ₂ -).

IR (liquid neat;cm ^-1 ): 2914(m), 2764(m), 1643(s), 1596(m), 1560(m), 1500(m), 1460(s), 1430(s), 1368(s), 1310(m), 1149(m), 1037(m), 960(m), 890(m), 832(s), 750(s), 618(m).

1-2: Preparation of cobalt complex C1

After dissolving ligand L1 (0.228 g, 1.00 mmol) obtained in Preparation Example 1-1 in absolute ethanol (10.0 mL), CoCl ₂ 6H ₂ O (0.238 g, 1.00 mmol) dissolved in absolute ethanol (10.0 mL) ) and reacted by stirring at room temperature for 24 hours. After completion of the reaction, the resulting green solid powder was filtered, washed twice with cold ethanol (20.0 mL), and washed three times with diethylether (20.0 mL). After washing, the product was dried in a vacuum oven to prepare cobalt complex C1 (0.258 g, 72%) represented by Formula 1a. The structure of the prepared cobalt complex C1 is shown in FIG.

Analysis calculated for C ₁₄ H ₁₆ C _l2 CoN ₂ O: C, 46.95%, H, 4.50%, N, 7.82%.

Found: C, 47.18%, H, 4.52%, N, 7.92%.

IR (solid neat;cm ^-1 ): 2941(w), 1641(m), 1505(m), 1435(m), 1381(m), 1333(m), 1072(s), 1042(s), 964(s), 905(m), 841(s), 807(s), 787(s), 749(s)

<Preparation Example 2: Preparation of Cobalt Complex C2>

2-1: Preparation of ligand L2

Ligand L2 was prepared by the following method with reference to J. Lee, H. Lee, S. Nayab and KB Yoon, Polyhedron , 2019, 158, 432-440.

2-Pyridinecarboxaldehyde (0.407 g, 3.8 mmol) was dissolved in CH ₂ Cl ₂ (50.0 mL), and a solution of N,N -Dimethylethylenediamine (0.335 g, 3.8 mmol) in CH ₂ Cl ₂ (50.0 mL) was dissolved therein. was mixed. The mixture was reacted by stirring at room temperature for 24 hours. After completion of the reaction, MgSO ₄ was added to the reactant, filtered through filter paper, and concentrated under reduced pressure to obtain ligand L2 (0.538 g, 80%) as an orange oil represented by Chemical Formula 4b.

¹ H NMR (CDCl ₃ , 500 MHz): δ 8.56 (d, 1H, J = 5.59 Hz -CH-CH=N-) 8.35 (s, 1H, CH ₂ -CH=NC-), 7.91 (d, 1H , J = 7.46 Hz -CH-CH=C-), 7.65 (t, 1H, J = 7.46 Hz -CH-CH=CH-), 7.23 (t, 1H, J = 5.59 Hz, -CH-CH=CH -), 3.73 (t, 2H, J = 7.49 Hz, -N-CH ₂ -CH ₂ -N=), 2.60 (t, 2H, J = 6.74 Hz, -N-CH ₂ -CH ₂ -N=) , 2.24 (s, 6H, -N-(CH ₃ ) ₂ ).

IR (liquid neat;cm ^-1 ): 2941(m), 2855(m), 2918(m), 2768(s), 1648(s), 1587(m), 1567(m), 1463(s), 1438(s), 1354(w), 1338(w), 1291(w), 1269(w), 1236(w), 1182(w), 1152(w), 989(m), 931(w), 855(m), 773(s), 743(s), 661(w), 616(m).

2-2: Preparation of cobalt complex C2

After dissolving the ligand L2 (0.886 g, 5.00 mmol) obtained in Preparation Example 2-1 in absolute ethanol (10.0 mL), CoCl ₂ 6H ₂ O (1.19 g, 1.00 mmol) dissolved in absolute ethanol (10.0 mL) ) and reacted by stirring at room temperature for 12 hours. After completion of the reaction, the resulting green solid powder was filtered, washed twice with cold ethanol (20.0 mL), and washed three times with diethylether (20.0 mL). After washing, the product was dried in a vacuum oven to prepare cobalt complex C2 (1.20 g, 78.2%) represented by Formula 1b. The structure of the prepared cobalt complex C2 is shown in FIG. 2 .

Analysis calculated for C ₁₀ H ₁₅ C _l2 CoN ₃ : C, 39.1%, H, 4.92%, N, 13.7%.

Found: C, 39.3%, H, 4.93%, N, 13.6%.

IR (solid neat; cm ^-1 ): 3551 (w), 2865 (w), 2837 (w), 2791 (w), 1642 (m), 1590 (m), 1441 (m), 1366 (w), 1336 (w), 1297 (m), 1262 (w), 1211 (m), 1155 (w), 1098 (w), 1066 (s), 1034 (m), 946 (m), 894 (m), 858 (w), 777 (s), 634 (m).

<Preparation Example 3: Preparation of Cobalt Complex C3>

3-1: Preparation of ligand L3

2-Quinolinecarboxaldehyde (0.600 g, 3.8 mmol) was dissolved in CH ₂ Cl ₂ (10.0 mL), and a solution of hexylamine (0.384 g, 3.8 mmol) in CH ₂ Cl ₂ (50.0 mL) was mixed therewith. The mixture was stirred and reacted for 48 hours while refluxing the solvent at 40 °C. After completion of the reaction, MgSO ₄ was added to the reactant, filtered through filter paper, and concentrated under reduced pressure to obtain ligand L3 (0.684 g, 75%) as dark red oil represented by Chemical Formula 4c.

¹ H NMR (CDCl ₃ , 500 MHz): δ 8.54 (s, 1H, -CH-CH=C-) 8.14 (s, 2H, -CH-CH=C-), 8.13 (s, 1H, -CH ₂ -CH=NC-), 7.78(s, 1H, -CH-CH=C-), 7.70 (t, 1H, J = 8.11 Hz, -CH-CH=CH-), 7.52 (t, 1H, J = 7.94 Hz, -CH-CH=CH-) 3.72 (t, 2H, J = 7.26 Hz, =N-CH ₂ -CH ₂ -), 1.75 (m, 2H, J = 7.60 Hz, -CH ₂ -CH ₂ -CH ₂ -N=), 1.39(m, 2H, J = 7.16 Hz, -CH ₂ -CH ₂ -CH ₂ -CH ₃ ), 1.32(m, 4H, J = 4.16 Hz, -CH ₂ -CH ₂ -CH ₂ -CH ₃ ), 1.32 (t, 3H, J = 6.97 Hz, -CH ₂ -CH ₂ -CH ₃ ).

IR (liquid neat; cm ^-1 ): 2926(s), 2856(s), 1645(m), 1596(m), 1561(m), 1502(m), 1460(m), 1431(m), 1371(m), 1313(m), 1142(w), 1114(w), 1017(w), 957(w), 893(w), 832(s), 749(s) 619(m).

3-2: Preparation of cobalt complex C3

After dissolving ligand L3 (0.240 g, 1.00 mmol) obtained in Preparation Example 3-1 in absolute ethanol (10.0 mL), CoCl ₂ 6H ₂ O (0.238 g, 1.00 mmol) dissolved in absolute ethanol (10.0 mL) ) and reacted by stirring at room temperature for 24 hours. After completion of the reaction, the resulting green solid powder was filtered, washed twice with cold ethanol (20.0 mL), and washed three times with diethylether (20.0 mL). After washing, the product was dried in a vacuum oven to prepare cobalt complex C3 (0.278 g, 75%) represented by formula 1c.

IR (solid neat; cm ^-1 ): 2952 (w), 2923 (w), 2854 (w), 1638 (w), 1508 (w), 1461 (w), 1434 (w), 1380 (w), 1346(w), 1303(w), 1208(w), 1124(w), 1043(w), 1019(w), 984(w), 883(w), 839(s), 784(s), 752(s), 724(w).

<Preparation Example 4: Preparation of Cobalt Complex C4>

4-1: Preparation of ligand L4

Ligand L4 was prepared by the following method with reference to C. Anderson, M. Crespo, M. Font-Bardia, A. Klein, X, Solans, Journal of Organometallic Chemistry , 601 (2000) 22-33.

2-thiophenecarboxaldehyde (2.24g, 20.0 mmol) was dissolved in CH ₂ Cl ₂ (50.0 mL), and a solution of N,N -Dimethylethylenediamine (1.76 g, 20.0 mmol) in CH ₂ Cl ₂ (50.0 mL) was dissolved therein. was mixed. The mixture was reacted by stirring at room temperature for 72 hours. After completion of the reaction, MgSO ₄ was added to the reactant, filtered through filter paper, and concentrated under reduced pressure to obtain ligand L4 (3.12 g, 78%) as a yellow oil represented by Formula 5a.

4-2: Preparation of cobalt complex C4

After dissolving the ligand L4 (0.364 g, 2.00 mmol) obtained in Preparation Example 4-1 in absolute ethanol (10.0 mL), CoCl ₂ 6H ₂ O (0.476 g, 2.00 mmol) dissolved in absolute ethanol (10.0 mL) ) and reacted by stirring at room temperature for 24 hours. After completion of the reaction, the resulting green solid powder was filtered, washed twice with cold ethanol (20.0 mL), and washed three times with diethylether (20.0 mL). After washing, the product was dried in a vacuum oven to prepare cobalt complex C4 (0.459 g, 75%) represented by Formula 2a. The structure of the prepared cobalt complex C4 is shown in FIG. 3 .

Analysis calculated for C ₉ H ₁₄ C _l2 NC ₂ oS: C, 34.63%, H, 4.52%, N, 8.98%. S, 10.27% Found: C, 34.72%, H, 4.53%, N, 8.89%. S, 10.45%

IR (solid neat;cm ^-1 ): 2978(m), 2902(m), 1616(s), 1454(s), 1423(s), 1391(s), 1338(s), 1255(m), 1219(m), 1053(s), 1011(s), 729(s).

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

Norbornene was polymerized using the cobalt complexes prepared in Preparation Examples 1 to 4 as catalysts, respectively.

First, the complex catalyst (15 μmol) was put into a Schlenk flask under argon and vacuum atmosphere, and then 5 ml of toluene (scavenger: MMAO) was added to dissolve the complex catalyst. 3.1 ml of denatured methylaluminoxane (MMAO) was injected therein, followed by stirring in a 90 °C bath for 30 minutes. In another Schlenk flask in the same atmosphere, 1.42 g of norbornene was added, 0.63 ml of tetralin and 15 ml of toluene were added, stirred in a 90 ° C bath for 30 minutes, and then the activated complex catalyst was injected and stirred in a 90 ° C bath for 18 hours. The reaction was carried out while stirring. Then, the reaction was terminated by injecting hexane (2 mL + 2 mL Ar), and the reaction polymer was added to a solution containing hexane (500 mL) and HCl (5 mL), followed by stirring for at least 30 minutes, and , and dried under vacuum to prepare a final polymer.

At this time, the results of the polymerization reaction were measured using NMR, and the results are shown in Table 1 as the yield and conversion rate of norbornene polymer for each catalyst.

division Conversion rate (%) transference number(%) Cobalt complex of Preparation Example 1 (C1) 78.2 68.0 Cobalt complex of Preparation Example 2 (C2) 70.6 93.1 Cobalt complex of Preparation Example 3 (C3) 46.7 83 Cobalt complex (C4) of Preparation Example 4 64.7 64.5

<Example 2: Preparation of methylnorbornene (MeNB) polymer>

Methylnorbornene was polymerized using the cobalt complexes of Preparation Examples 1 to 4 as catalysts, respectively. First, the complex catalyst (15 μmol) was added to a Schlenk flask under an argon and vacuum atmosphere, and then 20 ml of toluene (scavenger: MMAO) was added to dissolve the complex catalyst. 3.1 ml of denatured methylaluminoxane (MMAO) was injected therein, followed by stirring in a 90 °C bath for 30 minutes. 2.2 ml of methylnorbornene (MeNB) and 0.21 ml of tetralin were added thereto, followed by stirring in a 90 °C bath for 2 hours to carry out the reaction. Then, the reaction was terminated by injecting hexane (2 mL + 2 mL Ar), and the reaction polymer was added to a solution containing hexane (Hex) (500 mL) and HCl (5 mL), followed by stirring for at least 30 minutes. Then, the final polymer was prepared by vacuum drying.

At this time, the results of the polymerization reaction were measured using NMR, and the results are shown in Table 2 as the yield and conversion rate of methylnorbornene polymer for each catalyst.

division Conversion rate (%) transference number(%) Cobalt complex of Preparation Example 1 (C1) 8.6 30.8 Cobalt complex of Preparation Example 2 (C2) 22.6 40.8 Palladium complex of Preparation Example 3 (C3) 12.6 41.2 Palladium complex (C4) of Preparation Example 4 14.5 -

<Example 3: Preparation of a copolymer of norbornene (NB) and methylnorbornene (MeNB)>

Norbornene and methylnorbornene were copolymerized using the cobalt complexes prepared in Preparation Examples 1 to 4 as catalysts, respectively.

First, the complex catalyst (15 µmol) was added to a Schlenk flask under an argon and vacuum atmosphere, and then 5 ml of toluene (scavenger: MMAO) was added to dissolve the complex catalyst. 3.1 ml of denatured methylaluminoxane (MMAO) was injected therein, followed by stirring in a 90 °C bath for 30 minutes. In another Schlenk flask in the same atmosphere, 0.71 g of norbornene and 1.141 g of methylnorbornene (MeNB) were added, 15 ml of toluene and 0.21 ml of tetralin were added, dissolved by stirring in a 90 ° C bath for 30 minutes, and then activated as above The reaction was performed by injecting the complex catalyst and stirring for 18 hours in a 90 ° C bath. Then, the reaction was terminated by injecting hexane (2 mL + 2 mL Ar), and the reaction polymer was added to a solution containing hexane (Hex) (500 mL) and HCl (5 mL), followed by stirring for at least 30 minutes. was performed and dried under vacuum to prepare a final polymer.

At this time, the results of the polymerization reaction were measured using NMR, and the results are shown in Table 3 as yields and conversion rates of norbornene and methylnorbornene copolymers for each catalyst.

division Conversion rate (%) transference number(%) Complex of Preparation Example 1 (C1) 18.3
(NB:MeNB=30%:10%) 40 Complex of Production Example 2 (C2) 35.5
(NB:MeNB=47.2%:29%) 53.7 Complex of Preparation Example 3 (C3) 24.7
(NB:MeNB=4.1%:25.2%) 24 Complex of Production Example 4 (C4) 33.5
(NB:MeNB=30.7%:37.0%) 24

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

The present invention is not limited by the above-described embodiments and the accompanying drawings, and it is common in the technical field to which the present invention belongs that various substitutions, modifications, and changes are possible within the scope without departing from the technical spirit of the present invention. It will be clear to those who have knowledge.

Claims (12)

A cobalt complex catalyst containing an imine ligand for polymerization of a cyclic olefin-based monomer comprising at least one of a compound represented by Formula 1 and a compound represented by Formula 2 below:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
R ₁ to R ₄ are the same or different, and each independently a hydrogen atom; It is selected from the group consisting of a substituted or unsubstituted alkyl group,
X ₁ to X ₄ are the same or different, and each independently represents a halogen group;
L is -(CH ₂ ) _y - (where y is an integer from 1 to 5);
Z is selected from the group consisting of an oxygen atom, a nitrogen atom, a carbon atom, and -(CH ₂ )-;
n is an integer of 0 or 1, m is an integer of 0 to 3,
Dotted lines indicate the presence or absence of binding.
According to claim 1,
X ₁ to X ₄ in Chemical Formulas 1 and 2 are the same or different, and each independently represents Cl or Br.
According to claim 1,
R ₁ to R ₄ in Formulas 1 and 2 are the same or different, and are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. complex catalyst.
According to claim 1,
The compound represented by Formula 1 is a cobalt complex catalyst containing an imine ligand for polymerization of a cyclic olefin monomer, characterized in that it is represented by any one of the following Formulas 1a to 1c.
[Formula 1a]

[Formula 1b]

[Formula 1c]

According to claim 1,
The compound represented by Formula 2 is a cobalt complex catalyst containing an imine ligand for polymerization of a cyclic olefin-based monomer, characterized in that represented by Formula 2a below.

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 cobalt complex catalyst containing an imine ligand for polymerization of any one of claims 1 to 5.
According to claim 6,
The cyclic olefinic monomer is at least one selected from the group consisting of norbornene, dicyclopentadiene, cyclopentadiene, cyclopentene, cyclobutene, cyclohexene, cycloheptene, cyclooctene, and derivatives thereof. Method for producing olefin-based polymers.
According to claim 6,
Method for producing a cyclic olefin-based polymer, characterized in that the cyclic olefin-based monomer is a compound represented by the following formula (3):
[Formula 3]

In Formula 3,
n is an integer from 0 to 4;
R ₁₁ to R ₁₄ are the same or different, and each independently a hydrogen atom; halogen atom; hydroxy 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 selected from the group consisting of an acyl group having 1 to 10 carbon atoms.
According to claim 6,
The method for producing the cyclic olefin-based polymer is a method for producing a cyclic olefin-based polymer, characterized in that addition polymerization of the cyclic olefin-based monomer in the presence of a cocatalyst with an imine-based ligand-containing cobalt complex catalyst for polymerization of the cyclic olefin-based monomer.
According to claim 9,
The cocatalyst is modified methylaluminoxane (MMAO), trimethyl aluminum (TMA), triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL), dimethylchloro aluminum (Diethyl chloro aluminum, DMCA) and diethyl chloro aluminum (diethyl chloroaluminum, DECA) A method for producing a cyclic olefin-based polymer, characterized in that at least one selected from the group consisting of.
According to claim 10,
The cocatalyst is a method for producing a cyclic olefin-based polymer, characterized in that modified methylaluminoxane (MMAO).
According to claim 6,
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 is performed in at least one solvent selected from the group consisting of chloroethane.

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