KR20220114945A - Catalyst for Addition Polymerization of Polar Vinyl Monomers and Method for Preparing Polar Vinyl Polymer Using the Same - Google Patents

Abstract

The present invention relates to a catalyst for the addition polymerization of a monomer having a polar vinyl group and a preparation method of a polymer of a monomer having a polar vinyl group using the catalyst, and more particularly, to a preparation method of a polymer having a polar vinyl group in which a catalyst comprising a cobalt complex in which a cobalt halide compound is bonded to a bispyrazolyl ligand and an organic aluminum compound is used as the catalyst for the addition polymerization of a monomer having a polar vinyl group, and the addition polymerization of a monomer having a polar vinyl group is performed in the presence of the catalyst for the addition polymerization of a monomer having a polar vinyl group.

Description

Catalyst for addition polymerization of a monomer having a polar vinyl group and a method for preparing a polymer of a monomer having a polar vinyl group using the same

The present invention relates to a catalyst for addition polymerization of a monomer having a polar vinyl group and a method for preparing a polymer of a monomer having a polar vinyl group using the same. A polymer having a polar vinyl group is prepared by using a catalyst comprising a cobalt complex to which a cobalt compound is bonded and an organoaluminum compound, and addition polymerization of a monomer having a polar vinyl group in the presence of a catalyst for addition polymerization of a monomer having a polar vinyl group it's about how

Polymethyl methacrylate, which is a polymer of a monomer having a polar vinyl group, is a polymer of methyl methacrylate and is produced by methyl methacrylate alone or by copolymerization of methyl methacrylate and acrylate, and polymethyl methacrylate has transparency and It has excellent weather resistance as well as mechanical strength such as tensile strength and elastic modulus, and excellent physical properties such as surface gloss and chemical resistance, so it is widely used in various materials such as architecture, lighting, and film. And it is widely used for optical applications such as displays.

Catalysts for the polymerization of polymethyl methacrylate are well known by the prior art for catalytically polymerizing olefins or olefin copolymers, and many studies related to catalysts are still in progress.

Korean Patent Application Laid-Open No. 2003-0007830 discloses polymethyl methacrylate using a transition metal catalyst of a monoanionic phosphine ligand that includes Group 15 or Group 16 and is coordinated to a Group 3 to 11 transition metal or a lanthanide metal. discloses a method for producing an ethylene/polar monomer copolymer, including A manufacturing method is disclosed.

In addition, in US Patent No. 4,680,352, a catalyst in which the N atom of the ligand 4,7-diaza-2,9-dihydroxyimino-3,8-dimethyldeca-3,7-diene is coordinated to cobalt is used as a cobalt complex compound using methyl metabolite. Polymerization of acrylate, polymerization of methyl methacrylate and styrene, and polymerization of styrene and butyl methacrylate and hydroxyethyl methacrylate are disclosed. U.S. Patent No. 4,837,326 discloses amine, pyridine or Using a ligand selected from triphenylphosphine and a cobalt (II) complex of nitrilomethylidine as a catalyst, polymerization of methyl methacrylate, polymerization of methyl methacrylate and butyl acrylate, and polymerization of methyl methacrylate and ethyl acrylate It discloses, and describes obtaining a polymer having a low molecular weight by performing polymerization of methyl methacrylate, butyl acrylate, and styrene.

And in the literature [Vernon C. Gibson research team, Macromolecules. 2003, 36, 2591-2593], a complex having four coordination numbers (α-Diimine), that is, a complex in which N atoms and Cl atoms are coordinated to the Fe metal center, is catalyzed The polymerization of methyl methacrylate is disclosed as described in [Chunming Cui research team, Appl. Organometal. Chem 2010, 24, 82-85 [ Disclosed is the preparation of a methyl methacrylate polymer with high activity by activation with an aluminoxane (MAO) cocatalyst, and the prepared polymer of methyl methacrylate mainly exhibits syndiotacticity, has a high molecular weight, and has a narrow It shows that it has a molecular weight distribution.

See also Il Kim's team, Macromolecular Research. 2008, 16, 745-748] uses methylaluminoxane (MAO) as a co-catalyst for Bis(saicylaldiminate)Cobalt(II), that is, a catalyst in which N and O atoms are coordinated to a metal center, to increase the activity of the catalyst and increase the activity of the methyl A polymer of methacrylate was prepared, and as a result, a methyl methacrylate polymer having a syndiotacticity of 73.5% or more was obtained.

In the literature [Guo-Xin Jin's research team, Organometallics 2008, 27, 259-269], a new ligand was synthesized by coordinating two central metals with a divalent central metal to the ligand of 2,5-Diamino-1,4-benzoquinonediimines. By activating the iron and cobalt metal complex catalyst compound in which the N and O atoms of the ligand are coordinated to the two central metals nickel and copper with a methylaluminoxane (MAO) cocatalyst, copper did not produce a polymer, but nickel has a wide molecular weight distribution and Methyl methacrylate having a high molecular weight was polymerized. In the literature [Qing Wu research team, Organometallics 2003, 22, 4952-4957], a novel catalyst in which the N and O atoms of Bis(β-ketonamino), a chelating ligand, are coordinated to a nickel central metal, that is, a bivalent nickel metal catalyst, is methylaluminoxane Disclosed is the preparation of a polymer mainly having synthiotacticity by activation with a cocatalyst.

However, there has been no reported case in which polymerization performance of a metal catalyst is improved by using a catalyst including an organoaluminum compound and a cobalt complex in which a cobalt halide compound is bonded to a bispyrazolyl ligand during polymerization of a monomer having a polar vinyl group.

(Patent Constitution 0001) Korea Patent Publication No. 2003-0007830 (published on: January 23, 2003) Korea Patent Publication No. 2010-0004839 (published on: January 13, 2010) U.S. Patent No. 4,680,352 (Announcement Date: July 14, 1987) U.S. Patent No. 4,837,326 (Announcement Date: June 6, 1989)

Vernon C. Gibson, Macromolecules. 2003, 36, 2591-2593 Guo-Xin Jin, Organometallics 2008, 27, 259-269 Qing Wu, Organometallics 2003, 22, 4952-4957

An object of the present invention is to provide a catalyst for addition polymerization of a monomer having a polar vinyl group, which exhibits high polymerization activity in preparing a polymer of a monomer having a polar vinyl group.

In addition, another object of the present invention is to polymerize a monomer having a polar vinyl group in the presence of a catalyst for addition polymerization of a monomer having a polar vinyl group to prepare a polymer having a polar vinyl group with high polymerization activity of a monomer having a polar vinyl group. To provide a method for preparing a polymer.

In order to achieve the above object, one embodiment of the present invention is for addition polymerization of a monomer having a polar vinyl group, characterized in that it comprises a cobalt complex represented by the following formula (1) and an organoaluminum compound represented by the following formula (2) provides a catalyst.

[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,

[Formula 2]

In Formula 2, m is an integer from 1 to 10, and n is an integer from 1 to 10.

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 may be characterized as a substituent 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 of Formula 1 may be the same or different, and each independently Cl or Br.

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 Formula 1a or 1b.

[Formula 1a]

[Formula 1b]

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

[Formula 1c]

[Formula 1d]

[Formula 1e]

Formula 1 may be characterized in that it is represented by the following formula 1f or 1g.

[Formula 1f]

[Formula 1g]

Another embodiment of the present invention provides a method for preparing a polymer of a monomer having a polar vinyl group, comprising the step of addition polymerization of a monomer having a polar vinyl group in the presence of a catalyst for addition polymerization of the monomer having a polar vinyl group do.

In another preferred embodiment of the present invention, the monomer having a polar vinyl group may be at least one selected from the group consisting of vinyl acetate, acrylate and alkyl methacrylate, and the alkyl methacrylate is methyl methacrylate. can be characterized.

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, a catalyst for addition polymerization having high activity in polymerization of a monomer having a polar vinyl group can be provided, and a monomer having a polar vinyl group can be converted to high activity in the presence of the catalyst for addition polymerization of a monomer having a polar vinyl group. A polymer having a polar vinyl group can be prepared by polymerization.

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 addition polymerization of a monomer having a polar vinyl group, comprising a cobalt complex represented by the following formula (1) and an organoaluminum compound represented by the following formula (2).

[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,

[Formula 2]

In Formula 2, m is an integer from 1 to 10, and n is an integer from 1 to 10.

More specifically, the catalyst for addition polymerization of a monomer having a polar vinyl group according to the present invention has [A] the cobalt complex represented by Formula 1 as the main catalyst, and [B] The organoaluminum compound represented by Formula 2 is prepared included as a catalyst.

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.

Meanwhile, in the catalyst for addition polymerization of a monomer having a polar vinyl group of the present invention, the [B] organoaluminum compound as a co-catalyst may be represented by the following formula (2).

[Formula 2]

In this case, in Formula 2, m may be an integer of 1 to 10, and n may be an integer of 1 to 10.

The organoaluminum compound represented by Formula 2 reacts with a small amount of impurities and the cobalt complex represented by Formula 1 used as a main catalyst during the reaction to reduce the reaction activity, and only a small amount of impurities so that it can react with the monomer. By acting to remove by reaction with the monomer, it is possible to produce a polymer having a polar vinyl group in a high yield while showing excellent activity even in a small amount compared to the monomer, and after addition polymerization, the additional effort for removing the residual catalyst is much less than that of the conventional method has an advantage.

In this case, the [B] organoaluminum compound represented by the formula (2) may include 1 mol to 800 mol with respect to 1 mol of the cobalt complex represented by the [A] formula (1). If the [B] organoaluminum compound represented by Formula 2 is contained in an amount of less than 1 mol with respect to 1 mol of the cobalt complex, the polymerization reaction does not proceed or the polymerization yield is lowered, and 800 mol If it is exceeded, there may be a problem in that gelation proceeds due to the co-catalyst.

Such an organoaluminum compound represented by Formula 2 can be easily purchased in the market, and is good in terms of workability.

In another aspect, the present invention relates to a method for preparing a polymer of a monomer having a polar vinyl group, comprising the step of addition polymerization of a monomer having a polar vinyl group in the presence of a catalyst for polymerization of a monomer having a polar vinyl group.

The monomer having the polar vinyl group is selected from vinyl acetate, acrylate, acyl methacrylate, and methyl methacrylate, and may preferably be methyl methacrylate in terms of polymerization activity.

In the present invention, the above-described monomer having a polar vinyl group may be homopolymerized, or a monomer having two or more polar vinyl groups may be copolymerized, and the above-described monomer having a polar vinyl group and an olefinic monomer may be copolymerized. In this case, the olefinic monomer can be used without limitation as long as it is an olefinic monomer capable of addition polymerization with a monomer having a polar vinyl group. have.

In the case of polymerizing a monomer having a polar vinyl group using the catalyst for addition polymerization of a monomer having a polar vinyl group according to 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.

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 mass, filtered through filter paper, and concentrated under reduced pressure to obtain ligand L1 (4.44 g, 85%) as a colorless oily liquid represented by Chemical Formula 3a.

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 a cobalt complex C1 represented by Formula 1a (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 C2>

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 the reaction was completed, MgSO ₄ was added to the reaction product, filtered through filter paper, and then concentrated under reduced pressure. The ligand L2 as a white solid represented by Formula 3b (5.28 g, 80.2) %) was obtained.

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 %) represented by Formula 1b.

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, and after completion of the reaction, MgSO ₄ was added to the reaction mass, filtered through filter paper, and concentrated under reduced pressure. The ligand L3 as a colorless oil represented by Formula 3c (5.00 g, 76%) ) was obtained.

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 represented by Formula 1c (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 represented by Chemical Formula 3d.

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 %) of formula 1d.

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 represented by Formula 3f.

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 represented by Formula 1f 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 (0.78 g, 92% ) was prepared. 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 mass, filtered through filter paper, and concentrated under reduced pressure to obtain ligand L6 (5.2 g, 82%) as a white solid represented by Chemical Formula 3e.

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 represented by Formula 1e 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 (0.78 g, 88% ) was prepared. 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 then concentrated under reduced pressure to obtain ligand L7 (6.00 g, 76%) as a yellow oil represented by Chemical Formula 3g.

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 represented by Formula 1g in the same manner as in Preparation Example 3-2 using the ligand L7 (0.703 g, 2.00 mmol) of Preparation 7-1 instead of the ligand L3 of Preparation Example 3-2 (0.896 g, 92% ) was prepared. 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 methyl methacrylate (MMA) polymer>

Methyl methacrylate was polymerized using the cobalt complexes of Preparation Examples 1 to 7 as catalysts, respectively.

First, the cobalt complex (15 μmol) was added to a Schlenk flask under argon and vacuum atmosphere, and then 20 ml of toluene (scavenger: MMAO) was added to dissolve the cobalt complex. 3.1 ml (7.5 mmol, Al%) of modified methylaluminoxane (Lake Materials, MMAO-M, Hexane) was injected here, and then stirred in a 60° C. bath for 30 minutes. After stirring was completed, 0.63 ml of tetralin and 5 ml of methyl methacrylate (MMA) were added, respectively, 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 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 (C1) of Preparation Example 1, the yield was found to be 62%, Tg was 120.72 °C, and Mw in GPC was 11.24 (g / mol)×10 ⁵ , and the Mw/Mn value was found to be 3.32. In the case of the cobalt complex (C2) of Preparation Example 2, the yield was 18%, Tg was 122.01 ° C., Mw in GPC was 9.35 (g / mol) × 10 ⁵ , and Mw / Mn value was 2.91. In the case of the cobalt complex (C3) of Preparation Example 3, the conversion rate is 49%, the yield is 45%, Tg is 122.12 ° C., Mw is 10.82 (g / mol) × 10 ⁵ in GPC, Mw / Mn value is It was found to be 2.75.

In addition, in the case of the cobalt complex (C4) of Preparation Example 4, the conversion rate is 49%, the yield is 43%, Tg is 119.31 ° C., Mw is 9.97 (g / mol) × 10 ⁵ in GPC, Mw / Mn value was found to be 2.87, and in the case of the cobalt complex (C5) of Preparation Example 5, the conversion rate was 45%, the yield was 38%, Tg was 122.79 °C, and Mw in GPC was 10.79 (g / mol) × 10 ⁵ and the Mw / Mn value was found to be 2.32, and in the case of the cobalt complex (C6) of Preparation Example 6, the conversion rate was 23%, the yield was 18%, Tg was 120.21 °C, and Mw in GPC was 12.42 (g /mol)×10 ⁵ , and the Mw/Mn value was found to be 2.43. In the case of the cobalt complex (C7) of Preparation Example 7, the conversion rate is 20%, the yield is 11%, Tg is 122.52 °C, Mw in GPC is 3.19 (g / mol) × 10 ⁵ , and Mw / Mn value is It was found to be 8.30.

<Example 2: Preparation of copolymer of methyl methacrylate (MMA) and norbornene (NB)>

Methyl methacrylate and norbornene 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 (7.5 mmol, Al%) of modified methylaluminoxane (Lake Materials, MMAO-M, Hexane) was injected here, followed by stirring 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 (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 (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 3: Preparation of copolymer of methyl methacrylate (MMA) and dicyclopentadiene (DCPD)>

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 (7.5 mmol, Al%) of modified methylaluminoxane (Lake Materials, MMAO-M, Hexane) was injected thereto, and then stirred in a bath at 60° C. 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 thereto to dissolve, and then the activated The reaction was carried out by injecting a cobalt complex catalyst and stirring it in a 60 °C bath 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 (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 catalyst for addition polymerization having high activity in the polymerization of a monomer having a polar vinyl group, and by polymerizing a monomer having a polar vinyl group in the presence of the catalyst for addition polymerization, a polar vinyl group with high activity It was confirmed that a polymer having a group could be prepared.

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 (11)

A catalyst for addition polymerization of a monomer having a polar vinyl group, characterized in that it comprises a cobalt complex represented by the following formula (1) and an organoaluminum compound represented by the following formula (2):
[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 is 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, the dotted line indicates the presence or absence of a bond,
[Formula 2]

In Formula 2, m is an integer from 1 to 10, and n is an integer from 1 to 10.
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 catalyst for addition polymerization of a monomer having a polar vinyl group, characterized in that the substituent selected from the group consisting of a heteroaryl group having 2 to 20 carbon atoms having O, N or S substituted or unsubstituted.
According to claim 1,
X ₁ and X ₂ of Formula 1 are the same or different, and each independently represents Cl or Br. A catalyst for addition polymerization of a monomer having a polar vinyl group.
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. A catalyst for addition polymerization of a monomer having a polar vinyl group.
According to claim 1,
Chemical Formula 1 is a catalyst for addition polymerization of a monomer having a polar vinyl group, characterized in that it is represented by the following Chemical Formula 1a or 1b.
[Formula 1a]

[Formula 1b]

According to claim 1,
Chemical Formula 1 is a catalyst for addition polymerization of a monomer having a polar vinyl group, 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,
Chemical Formula 1 is a catalyst for addition polymerization of a monomer having a polar vinyl group, characterized in that it is represented by the following Chemical Formula 1f or 1g.
[Formula 1f]

[Formula 1g]

A method for preparing a polymer of a monomer having a polar vinyl group, comprising the step of addition polymerization of a monomer having a polar vinyl group in the presence of a catalyst for addition polymerization of a monomer having a polar vinyl group according to any one of claims 1 to 7.
9. The method of claim 8,
The method for producing a polymer of a monomer having a polar vinyl group, characterized in that the monomer having a polar vinyl group is at least one selected from the group consisting of vinyl acetate, acrylate and alkyl methacrylate.
10. The method of claim 9,
The method for producing a polymer of a monomer having a polar vinyl group, characterized in that the alkyl methacrylate is methyl methacrylate.
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 polymer of a monomer having a polar vinyl group, characterized in that the polymerization is performed in one or more solvents selected from the group consisting of chloroethane.

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