KR102513130B1 - Complex Catalyst Containing Amine Ligand 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 complex 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, and more particularly, to a catalyst for addition polymerization of a monomer having a polar vinyl group, which is halogenated to an amine-based ligand It relates to a method for producing a polymer having a polar vinyl group by addition polymerization of a monomer having a polar vinyl group in the presence of a complex catalyst to which a cobalt or palladium halide compound is bonded and the complex catalyst for addition polymerization of the monomer having a polar vinyl group. .

Description

Complex Catalyst Containing Amine Ligand for Addition Polymerization of Polar Vinyl Monomers and Method for Preparing Polar Vinyl Polymer Using the Same }

The present invention relates to a complex catalyst containing an amine-based ligand 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, and more particularly, to a complex catalyst for addition polymerization of a monomer having a polar vinyl group A method for preparing a polymer having a polar vinyl group by using a complex in which a halogenated metal compound is bonded to an amine-based ligand and adding a monomer having a polar vinyl group in the presence of a complex catalyst for addition polymerization of the monomer having a polar vinyl group will be.

Polymethyl methacrylate, a polymer of monomers having a polar vinyl group, is a polymer of methyl methacrylate and is prepared by methyl methacrylate alone or by copolymerization of methyl methacrylate and acrylate, and polymethyl methacrylate has transparency and In addition to excellent weather resistance, mechanical strength such as tensile strength and modulus of elasticity, surface gloss, and chemical resistance are excellent, so they are widely used in various materials such as architecture, lighting, and films. In particular, lenses and transparent substrates due to excellent transparency And it is widely used for optical purposes such as displays.

Catalysts for polymerization of such polymethyl methacrylate are well known in the prior art for catalytically polymerizing olefins or olefin copolymers, and many studies related to catalysts are currently being conducted.

Korean Patent Publication No. 2003-0007830 discloses polymethyl methacrylate using a transition metal catalyst of a monoanionic phosphine ligand coordinated to a group 15 or 16 group and coordinated to a group 3 to 11 transition metal or a lanthanide metal Disclosed is a method for preparing an ethylene/polar monomer copolymer, including Korean Patent Publication No. 2010-0004839, which uses a novel iron complex having a cyclic amine compound as a ligand as a catalyst to polymerize a radical polymerizable monomer. A manufacturing method is disclosed.

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

And in the literature [Vernon C. Gibson research team, Macromolecules.2003, 36, 2591-2593], a catalyzed (α-Dimine)iron complex with four coordination numbers, that is, a complex in which N atoms and Cl atoms are coordinated to the Fe metal center As a result, polymerization of methyl methacrylate is initiated, and literature [Chunming Cui research team, Appl. Organometal. Chem 2010, 24, 82-85] applied a 2-(N-arylimino)prrolide ligand to nickel as an iron and cobalt metal complex catalyst, using a non-metallocene compound in which N atoms are coordinated to the central metal as the main catalyst to produce methyl It discloses the production of a highly active methyl methacrylate polymer by activation with an aluminoxane (MAO) cocatalyst, and the prepared methyl methacrylate polymer 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 research team, Macromolecular Research. 2008, 16, 745-748] used Bis(saicylaldiminate)Cobalt(II), that is, a catalyst in which N atoms and O atoms are coordinated at the metal center, as a co-catalyst, and methyl aluminoxane (MAO) was used to increase the catalytic activity, thereby increasing the methyl A polymer of methacrylate was prepared, and as a result, a methyl methacrylate polymer having a syndiotacticity of 73.5% or more could be obtained.

In the literature [Guo-Xin Jin research team, Organometallics 2008, 27, 259-269], a new ligand is synthesized by coordinating two central metals whose central metals are divalent to the ligands of 2,5-Diamino-1,4-benzoquinonediimines, that is, An iron and cobalt metal complex catalyst compound in which the N and O atoms of the ligand are coordinated to two central metals, nickel and copper, was activated with methylaluminoxane (MAO) as a cocatalyst to prepare copper polymers, but nickel had a wide molecular weight distribution and Methyl methacrylate with a high molecular weight was polymerized. In the literature [Qing Wu research team, Organometallics 2003, 22, 4952-4957], a new catalyst in which N atoms and O atoms of Bis(β-ketonamino), a chelating ligand, are coordinated to a nickel central metal, that is, a divalent nickel metal catalyst, is methylaluminoxane It is disclosed to prepare a polymer having mainly synthiotacticity by activation with a cocatalyst.

However, when polymerizing a monomer having a polar vinyl group, there has been no report on an example in which the polymerization performance of a metal catalyst is improved by using a complex catalyst in which a halogenated cobalt compound or a halogenated palladium compound is bonded to an amine-based ligand.

(Patent Division 0001) Korea Patent Publication No. 2003-0007830 (published date: 2003.01.23) Korean Patent Publication No. 2010-0004839 (published date: 2010.01.13) US Patent Registration No. 4,680,352 (Announcement date: 1987.07.14) US Patent No. 4,837,326 (Announcement Date: 1989.06.06)

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 complex catalyst containing an amine-based ligand 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 a monomer having a polar vinyl group capable of producing a polymer having a polar vinyl group with high polymerization activity by polymerizing a monomer having a polar vinyl group in the presence of a complex catalyst for addition polymerization of the monomer having a polar vinyl group. It is to provide a method for producing a polymer of.

In order to achieve the above object, one embodiment of the present invention An amine-based ligand-containing complex catalyst for addition polymerization of a monomer having a polar vinyl group is provided, which comprises a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, M is palladium or cobalt, X ₁ and X ₂ are the same or different, each independently selected from the group consisting of a halogen group, and Z is an oxygen atom, a sulfur atom and -(CH ₂ )- It is selected from the group, m is an integer from 0 to 3.

In a preferred embodiment of the present invention, X ₁ and X ₂ of Formula 1 may be the same or different, and may each independently represent a chlorine atom (Cl) or a bromine atom (Br).

In a preferred embodiment of the present invention, the compound represented by Formula 1 may be characterized in that it is a compound represented by any one of Formulas 1a, 1b and 1c.

[Formula 1a]

[Formula 1b]

[Formula 1c]

In a preferred embodiment of the present invention, the compound represented by Chemical Formula 1 may be characterized in that it is a compound represented by any one of Chemical Formulas 1d, 1e and 1f below.

[Formula 1d]

[Formula 1e]

[Formula 1f]

Another embodiment of the present invention is 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 complex catalyst containing an amine-based ligand for addition polymerization of the monomer having a polar vinyl group. A method for preparing a polymer is provided.

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

In another preferred embodiment of the present invention, the alkyl methacrylate may be characterized in that methyl methacrylate.

In another preferred embodiment of the present invention, the method for producing a polymer of a monomer having a polar vinyl group is addition polymerization of a monomer having a polar vinyl group in the presence of a cocatalyst with an amine-based ligand-containing complex catalyst for addition polymerization of a monomer having a polar vinyl group It can be characterized by doing.

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 complex catalyst containing an amine-based ligand for addition polymerization having high activity in polymerization of monomers having a polar vinyl group, and the presence of a complex catalyst containing an amine-based ligand for addition polymerization of a monomer having a polar vinyl group A polymer having a polar vinyl group can be prepared by polymerizing a monomer having a polar vinyl group with high activity under

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.

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 an amine-based ligand-containing complex catalyst for addition polymerization of a monomer having a polar vinyl group, characterized in that it comprises a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, M is palladium or cobalt, X ₁ and X ₂ are the same or different, each independently selected from the group consisting of a halogen group, and Z is an oxygen atom, a sulfur atom or a group consisting of -(CH ₂ )- It is selected from, m is an integer from 0 to 3.

In X ₁ and X ₂ of Formula 1, the halogen group may be one or more selected from the group consisting of a chlorine atom (Cl), a bromine atom (Br), and an iodine atom (I), preferably a chlorine atom (Cl) Or it may be a bromine atom (Br).

In addition, m in Formula 1 is an integer of 0 to 3, preferably m may be an integer of 0 to 2, and Z in Formula 1 is an oxygen atom, a sulfur atom, or a group consisting of -(CH ₂ )- may be selected, preferably an oxygen atom or -(CH ₂ )-.

Specifically, the complex catalyst for monomer polymerization having a polar vinyl group according to an embodiment of the present invention is a complex catalyst in which an aminopyridine ligand or an aminoquinolyl ligand and a halogenated cobalt compound are bonded, respectively, and is represented by the following Chemical Formulas 1a, 1b, and 1c At least one of the indicated compounds may be included.

[Formula 1a]

[Formula 1b]

[Formula 1c]

In addition, the complex catalyst for monomer polymerization having a polar vinyl group according to another embodiment of the present invention is a complex catalyst in which an aminopyridine ligand or an aminoquinolyl ligand and a halogenated palladium compound are bonded, respectively, and is represented by Formula 1d, Formula 1e, and Formula 1f It may contain at least one of the compounds.

[Formula 1d]

[Formula 1e]

[Formula 1f]

The complex catalyst represented by Chemical Formula 1 may be prepared by reacting an amine-based derivative ligand represented by Chemical Formula 3 with a cobalt halide or a palladium halide precursor. In this case, the reaction between the amine-based derivative ligand and the cobalt halide or palladium 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 3]

In Formula 3, since m and Z are substantially the same as m and Z described in Formula 1, overlapping detailed descriptions are omitted.

Specifically, the compound represented by Formula 3 may be, for example, at least one of the compounds represented by Formulas 3a, 3b and Formula 3c below.

[Formula 3a]

[Formula 3b]

[Formula 3c]

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

In addition, the palladium halide precursor may be palladium chloride, brompalladium, iodopalladium, etc., preferably palladium chloride and brompalladium, more preferably palladium chloride.

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

In another aspect, the present invention is a method for producing 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 complex catalyst containing an amine-based ligand for polymerization of the above-described monomer having a polar vinyl group It is about.

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

In the present invention, the monomer having a polar vinyl group may be homopolymerized, or monomers having two or more polar vinyl groups may be copolymerized, or the monomer having a polar vinyl group may be copolymerized with an olefinic monomer. At this time, 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, and in terms of physical properties of the prepared polymer, norbornene, dicyclopentadiene, etc. there is.

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, a liquid phase or a gaseous 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, well-known compounds widely used in the prior art of catalytically polymerizing (co)polymers of monomers having polar vinyl groups can be 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-chloromethyl pyridine hydrochloride (3.28 g, 20.0 mmol) was dissolved in distilled water (20.0 mL), and morpholine (1.742 g, 20.0 mmol) dissolved in distilled water (20.0 mL) and NaOH (1.60 g, 40.0 mmol) were dissolved therein. After addition, the reaction was carried out by stirring at room temperature for 5 days. Here, CH ₂ Cl ₂ (50.0 mL) was added to extract the reaction product, MgSO ₄ was added to the reactant, filtered with filter paper, and concentrated under reduced pressure to form ligand L1 (2.77 g of dark red oil represented by Chemical Formula 3a). , 78%) was obtained.

¹ H-NMR (CDCl ₃ , 500 MHz): δ 8.58 (d, 1H, J = 4.91 Hz, -N-CH=CH-), 7.65 (t, 1H, J = 7.55 Hz, -CH=CH-CH =), 7.40 (d, 1H, J = 7.79 Hz, -CH=CH-C-), 7.17 (t, 1H, J = 7.59 Hz, -CH=CH-CH=), 3.74 (t, 4H, J = 4.59 Hz, -O-CH ₂ -CH ₂ -), 3.66(s, 2H, -NCH ₂ N-), 2.51(t, 4H, J = 4.60 Hz, -N-CH ₂ -CH ₂ -)

IR (liquid neat;cm ^-1 ): 2958(w), 2854(m), 2809(m), 1590(m), 1473(m), 1432(m), 1287(m), 1263(m), 1139(m), 1113(s), 1069(m), 1040(m), 1005(s), 863(m), 807(s), 757(s).

1-2: Preparation of cobalt complex C1

After dissolving ligand L1 (0.356 g, 2.00 mmol) obtained in Preparation Example 1-1 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 blue 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 (0.493 g, 80%) represented by Formula 1a. The structure of the prepared cobalt complex C1 is shown in FIG.

IR (solid neat; cm ^-1 ): 2978(m), 2901(m), 1607(m), 1443(s), 1296(s), 1108(s), 1089(s), 1062(s), 1028(s), 992(s), 867(s), 775(s).

<Preparation Example 2: Preparation of Cobalt Complex C2>

2-1: Preparation of ligand L2

2-chloromehtyl quinoline hydrochloride (4.282 g, 20.0 mmol) was dissolved in distilled water (20.0 mL), and morpholine (1.742 g, 20.0 mmol) dissolved in distilled water (20.0 mL) and NaOH (1.60 g, 40.0 mmol) were dissolved therein. After addition, the reaction was carried out by stirring at room temperature for 5 days. Here, CH ₂ Cl ₂ (50.0 mL) was added to extract the reaction product, MgSO ₄ was added to the reactant, filtered with filter paper, and concentrated under reduced pressure to form ligand L2 (2.94 g of dark red oil represented by Formula 3b). , 65%) was obtained.

¹ H-NMR (CDCl ₃ , 500 MHz): δ 8.14 (d, 1H, J = 8.81 Hz, -CH=CH-C-), 8.09 (d, 1H, J = 8.28 Hz, -CH=CH-C -), 7.81 (d, 1H, J = 8.43 Hz, -CH=CH-C-), 7.70 (t, 1H, J = 7.59 Hz, -CH=CH-CH=), 7.65 (d, 1H, J = 8.66 Hz, -CH=CH-C-), 7.52 (t, 1H, J = 7.36 Hz, -CH=CH-CH=), 3.86(s, 2H, -NCH ₂ N-), 3.76 (t, 4H, J = 4.59 Hz, -O-CH ₂ -CH ₂ -), 2.57 (t, 4H, J = 4.60 Hz, -N-CH ₂ -CH ₂ -).

2-2: Preparation of cobalt complex C2

After dissolving the ligand L2 (0.456 g, 2.00 mmol) obtained in Preparation Example 2-1 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 blue 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 (0.520 g, 72%) represented by Formula 1b. The structure of the prepared cobalt complex C2 is shown in FIG. 2 .

IR (solid neat; cm ^-1 ): 2891(w), 2844(w), 1601(m), 1513(m), 1437(m), 1308(m), 1129(s), 1102(s), 994(s), 933(m), 871(s), 827(s), 784(s), 755(s).

<Preparation Example 3: Preparation of Cobalt Complex C3>

3-1: Preparation of ligand L3

2-chloromehtyl quinoline hydrochloride (4.282 g, 20.0 mmol) was dissolved in distilled water (20.0 mL), and piperidine (1.703 g, 20.0 mmol) and NaOH (1.60 g, 40.0 mmol) dissolved in distilled water (20.0 mL) were added thereto. After addition, the reaction was carried out by stirring at room temperature for 5 days. CH ₂ Cl ₂ (50.0 mL) was added thereto to extract the reaction product, MgSO ₄ was added to the reactant, filtered with filter paper, and concentrated under reduced pressure to form a brown oil ligand L3 represented by Formula 3c (2.665 g, 59%) was obtained.

¹ H-NMR (CDCl ₃ , 500 MHz): δ 8.12 (d, 1H, J = 8.55 Hz, -CH=CH-C-), 8.07 (d, 1H, J = 8.55 Hz, -CH=CH-C -), 7.80 (d, 1H, J = 8.08 Hz, -CH=CH-C-), 7.70-7.66 (m, 2H, -CH=CH-CH=, -CH=CH-C-), 7.51 ( t, 1H, J = 7.58 Hz, -CH=CH-CH=), 3.81 (s, 2H, -C-CH ₂ -N-), 2.49 (m, 4H, -N-CH ₂ -CH ₂ -) , 2.57 (quint, 4H, J = 5.61 Hz, -CH ₂ -CH ₂ -CH ₂ -), 2.57 (quint, 2H, J = 5.73 Hz, -CH ₂ -CH ₂ -CH ₂ -)

3-2: Preparation of cobalt complex C3

After dissolving ligand L3 (0.452 g, 2.00 mmol) obtained in Preparation Example 3-1 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 blue 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 (0.588 g, 83%) represented by formula 1c.

IR (solid neat; cm ^-1 ): 2943(m), 2918(w), 2856(m), 1602(m), 1510(m), 1453(m), 1086(s), 952(s), 829(s), 780(s), 755(s), 641(s).

<Preparation Example 4: Preparation of palladium complex C4>

4-1: Preparation of ligand L4

2-chloromethyl pyridine hydrochloride (3.28 g, 20.0 mmol) was dissolved in distilled water (20.0 mL), and morpholine (1.742 g, 20.0 mmol) dissolved in distilled water (20.0 mL) and NaOH (1.60 g, 40.0 mmol) were dissolved therein. After addition, the reaction was carried out by stirring at room temperature for 5 days. Here, CH ₂ Cl ₂ (50.0 mL) was added to extract the reaction product, MgSO ₄ was added to the reactant, filtered with filter paper, and concentrated under reduced pressure to form ligand L4 (2.77 g of dark red oil represented by Formula 3a). , 78%) was obtained.

¹ H-NMR (CDCl ₃ , 500 MHz): δ 8.58 (d, 1H, J = 4.91 Hz, -N-CH=CH-), 7.65 (t, 1H, J = 7.55 Hz, -CH=CH-CH =), 7.40 (d, 1H, J = 7.79 Hz, -CH=CH-C-), 7.17 (t, 1H, J = 7.59 Hz, -CH=CH-CH=), 3.74 (t, 4H, J = 4.59 Hz, -O-CH ₂ -CH ₂ -), 3.66(s, 2H, -NCH ₂ N-), 2.51(t, 4H, J = 4.60 Hz, -N-CH ₂ -CH ₂ -)

IR (liquid neat;cm ^-1 ): 2958(w), 2854(m), 2809(m), 1590(m), 1473(m), 1432(m), 1287(m), 1263(m), 1139(m), 1113(s), 1069(m), 1040(m), 1005(s), 863(m), 807(s), 757(s).

4-2: Preparation of palladium complex C4

After dissolving ligand L4 (0.356 g, 2.00 mmol) obtained in Preparation Example 4-1 in absolute ethanol (10.0 mL), Pd(MeCN) ₂ Cl ₂ (0.518 g, 2.00 mL) dissolved in absolute ethanol (10.0 mL). mmol) and reacted by stirring at room temperature for 24 hours. After completion of the reaction, the resulting yellow 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 (0.562 g, 79%) represented by formula 1d.

¹ H-NMR (CDCl ₃ , 500 MHz): δ 8.82 (d, 1H, J = 6.00 Hz, -N-CH=CH-), 8.14 (t, 1H, J = 7.39 Hz, -CH=CH-CH =), 7.72(d, 1H, J = 7.39 Hz, -CH=CH-C-), 7.57 (t, 1H, J = 6.73 Hz, -CH=CH-CH=), 4.81(s, 2H, - C-CH ₂ -N-), 3.92(t, 2H, J = 12.13 Hz, -O-CH ₂ -CH ₂ -), 3.85(t, 2H, J = 13.46 Hz, -O-CH ₂ -CH ₂ -), 3.61 (d, 2H, J = 12.47 Hz, -N-CH ₂ -CH ₂ -), 2.97 (d, 2H, J = 13.06 Hz, -N-CH ₂ -CH ₂ -).

IR (solid neat; cm ^-1 ): 2978(m), 2902(m), 2866(m), 1607(m), 1484(m), 1448(m), 1423(m), 1368(m), 1286(m), 1219(m), 1110(s), 1054(s), 964(s), 868(s), 820(m), 778(s), 662(m).

<Preparation Example 5: Preparation of Palladium Complex C5>

5-1: Preparation of ligand L5

2-chloromehtyl quinoline hydrochloride (4.282 g, 20.0 mmol) was dissolved in distilled water (20.0 mL), and morpholine (1.742 g, 20.0 mmol) dissolved in distilled water (20.0 mL) and NaOH (1.60 g, 40.0 mmol) were dissolved therein. After addition, the reaction was carried out by stirring at room temperature for 5 days. Here, CH ₂ Cl ₂ (50.0 mL) was added to extract the reaction product, MgSO ₄ was added to the reactant, filtered with filter paper, and concentrated under reduced pressure to form ligand L5 (2.94 g of dark red oil represented by Formula 3b). , 65%) was obtained.

¹ H-NMR (CDCl ₃ , 500 MHz): δ 8.14 (d, 1H, J = 8.81 Hz, -CH=CH-C-), 8.09 (d, 1H, J = 8.28 Hz, -CH=CH-C -), 7.81 (d, 1H, J = 8.43 Hz, -CH=CH-C-), 7.70 (t, 1H, J = 7.59 Hz, -CH=CH-CH=), 7.65 (d, 1H, J = 8.66 Hz, -CH=CH-C-), 7.52 (t, 1H, J = 7.36 Hz, -CH=CH-CH=), 3.86(s, 2H, -NCH ₂ N-), 3.76 (t, 4H, J = 4.59 Hz, -O-CH ₂ -CH ₂ -), 2.57 (t, 4H, J = 4.60 Hz, -N-CH ₂ -CH ₂ -).

5-2: Preparation of palladium complex C5

After dissolving ligand L5 (0.456 g, 2.00 mmol) obtained in Preparation Example 5-1 in absolute ethanol (10.0 mL), Pd(MeCN) ₂ Cl ₂ (0.518 g, 2.00 mL) dissolved in absolute ethanol (10.0 mL). mmol) and reacted by stirring at room temperature for 24 hours. After completion of the reaction, the resulting yellow 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 palladium complex C5 (0.674 g, 83%) represented by Formula 1e.

IR (solid neat;cm ^-1 ): 2980(m), 2903(w), 2860(w), 1514(m), 1435(m), 1112(s), 1054(s), 969(m), 860(s), 831(s), 777(m), 755(s), 665(s).

<Preparation Example 6: Preparation of palladium complex C6>

6-1: Preparation of ligand L6

2-chloromehtyl quinoline hydrochloride (4.282 g, 20.0 mmol) was dissolved in distilled water (20.0 mL), and piperidine (1.703 g, 20.0 mmol) and NaOH (1.60 g, 40.0 mmol) dissolved in distilled water (20.0 mL) were added thereto. After addition, the reaction was carried out by stirring at room temperature for 5 days. CH ₂ Cl ₂ (50.0 mL) was added thereto to extract the reaction product, MgSO ₄ was added to the reactant, filtered with filter paper, and concentrated under reduced pressure to form a brown oil ligand L6 represented by Formula 3c (2.665 g, 59%) was obtained.

¹ H-NMR (CDCl ₃ , 500 MHz): δ 8.12 (d, 1H, J = 8.55 Hz, -CH=CH-C-), 8.07 (d, 1H, J = 8.55 Hz, -CH=CH-C -), 7.80 (d, 1H, J = 8.08 Hz, -CH=CH-C-), 7.70-7.66 (m, 2H, -CH=CH-CH=, -CH=CH-C-), 7.51 ( t, 1H, J = 7.58 Hz, -CH=CH-CH=), 3.81 (s, 2H, -C-CH ₂ -N-), 2.49 (m, 4H, -N-CH ₂ -CH ₂ -) , 2.57 (quint, 4H, J = 5.61 Hz, -CH ₂ -CH ₂ -CH ₂ -), 2.57 (quint, 2H, J = 5.73 Hz, -CH ₂ -CH ₂ -CH ₂ -)

6-2: Preparation of palladium complex C6

After dissolving ligand L6 (0.452 g, 2.00 mmol) obtained in Preparation Example 6-1 in absolute ethanol (10.0 mL), Pd(MeCN) ₂ Cl ₂ (0.518 g, 2.00 mL) dissolved in absolute ethanol (10.0 mL). mmol) and reacted by stirring at room temperature for 24 hours. After completion of the reaction, the resulting yellow 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 palladium complex C6 (0.580 g, 72%) represented by Formula 1f.

IR (solid neat; cm ^-1 ): 2983(w), 2940(m), 2851(w), 1598(m), 1516(m), 1456(m), 1437(m), 1029(m), 865(s), 824(s), 786(m), 746(m).

<Example 1: Preparation of methyl methacrylate (MMA) polymer>

Methyl methacrylate was polymerized using the complexes of Preparation Examples 1 to 6 as catalysts, respectively.

First, the 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 complex. Here, 3.1 ml (7.5 mmol, Al%) of denatured methylaluminoxane (Lake Materials MMAO-M, Methylcychlohexane) was injected, followed by stirring in a 90 °C bath for 30 minutes. After completion of stirring, 0.63 ml of tetralin and 5 ml of methyl methacrylate (MMA) were added, respectively, and the reaction was performed by stirring in a 90 ° C bath for 2 hours. 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. . Thereafter, the final polymer was prepared by drying in a vacuum oven after a vacuum filter.

At this time, the results of the polymerization reaction were measured using NMR, thermal measurement (DSC) and gel permeation chromatography, and the results are shown in Table 1 as the yield and conversion rate of methyl methacrylate polymer for each complex. It was expressed as the glass transition temperature (Tg) and molecular weight distribution (PDI) of the methyl methacrylate polymer.

division Conversion rate (%) transference number(%) Tg(℃) PDI Cobalt complex of Preparation Example 1 (C1) 49 58 120.31 15.84 Cobalt complex of Preparation Example 2 (C2) 56 56 121.16 44.56 Cobalt complex of Preparation Example 3 (C3) 18 36 115.16 2.53 Palladium complex (C4) of Preparation Example 4 51 73 119.39 36.31 Palladium complex (C5) of Preparation Example 5 61 73 120.26 69.38 Palladium complex of Preparation Example 6 (C6) 59 62 120.40 2.76

Therefore, according to the present invention, it is possible to provide a complex catalyst for addition polymerization having high activity in polymerization of a monomer having a polar vinyl group, and polymerizing a monomer having a polar vinyl group in the presence of the complex catalyst for addition polymerization to achieve high activity. It was confirmed that a polymer having a polar vinyl 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 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 (11)

An amine-based ligand-containing complex catalyst for addition polymerization of a monomer having a polar vinyl group, characterized in that it comprises a compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
M is palladium or cobalt,
X ₁ and X ₂ are the same or different, and are each independently selected from the group consisting of a halogen group;
Z is selected from the group consisting of an oxygen atom, a sulfur atom, and -(CH ₂ )-;
m is an integer from 0 to 3;
According to claim 1,
X ₁ and X ₂ in Formula 1 are the same or different, and each independently represents a chlorine atom (Cl) or a bromine atom (Br). An amine-based ligand-containing complex catalyst for addition polymerization of a monomer having a polar vinyl group.
According to claim 1,
The compound represented by Formula 1 is an amine-based ligand-containing complex catalyst for addition polymerization of monomers having a polar vinyl group, characterized in that the compound represented by any one of Formulas 1a, 1b and 1c below.
[Formula 1a]

[Formula 1b]

[Formula 1c]

According to claim 1,
The compound represented by Formula 1 is an amine-based ligand-containing complex catalyst for addition polymerization of monomers having a polar vinyl group, characterized in that the compound represented by any one of Formulas 1d, 1e and 1f below.
[Formula 1d]

[Formula 1e]

[Formula 1f]

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 complex catalyst containing an amine-based ligand for addition polymerization of the monomer having a polar vinyl group according to any one of claims 1 to 4 Polymer manufacturing method of.
According to claim 5,
The monomer having a polar vinyl group is a method for producing a polymer of a monomer having a polar vinyl group, characterized in that at least one selected from the group consisting of vinyl acetate, acrylate and alkyl methacrylate.
According to claim 6,
The alkyl methacrylate is a method for producing a polymer of a monomer having a polar vinyl group, characterized in that methyl methacrylate.
According to claim 5,
The method for producing a polymer of a monomer having a polar vinyl group includes addition polymerization of a monomer having a polar vinyl group in the presence of a cocatalyst together with an amine-based ligand-containing complex catalyst for addition polymerization of a monomer having a polar vinyl group. A method for producing a polymer of monomers.
According to claim 8,
The cocatalyst 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 polymer of a monomer having a polar vinyl group, characterized in that at least one selected from the group consisting of.
According to claim 9,
The cocatalyst is a method for producing a polymer of a monomer having a polar vinyl group, characterized in that modified methylaluminoxane (MMAO).
According to claim 5,
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 preparing a polymer of a monomer having a polar vinyl group, characterized in that the polymerization is performed in at least one solvent selected from the group consisting of chloroethane.

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