KR20100035254A - Catalyst and coordination polymer of dicyclopentadiene - Google Patents

Abstract

PURPOSE: A catalyst for coordination polymerization of dicyclopentadiene is provided to prepare a dicyclopentadiene polymer with high solubility to a non-polar solvent and improved properties by coordinate polymerization. CONSTITUTION: A polymerization catalyst comprises at least one kind of Group 10 transition metal oxide selected from the compounds represented by chemical formula 1, 2 or 3, and an aluminumoxy compound. In chemical formulas, R is C1-8 alkyl group or aryl group; R^1 is C1-8 alkyl group, aryl group, and combinations thereof containing heteroatom(N or O); L is pyridine or MR'3, wherein M is N, P or As; R' is C1-4 alkyl group or C6-8 aryl group; R^3 is C1-4 alkyl group or C6-8 aryl group; and n is an integer of 1-2.

Description

Catalyst for dicyclopentadiene coordination polymerization and coordination polymer of dicyclopentadiene {Catalyst and Coordination Polymer of Dicyclopentadiene}

The present invention relates to a catalyst for dicyclopentadiene coordination polymerization and a copolymer of dicyclopentadiene obtained using the same.

Dicyclopentadiene (hereinafter abbreviated as DCPD) polymer has high impact strength and modulus and is a large complex by cross-linked thermosetting polymer by reaction injection molding (RIM). It is a polymer suitable for various applications such as the production of shaped objects.

One example of the application of DCPD polymers to the RIM is as schematically shown in FIG. 1.

RIM is a process that polymerizes in a mold by mixing two or more reactant portions of low viscosity. The joined reactants are easily turned into solid insoluble objects in the mold. Since this process requires only low pressure, the mold is inexpensive and easily deformable. Low viscosity monomers do not require large extruders and molds, and can be much lower than injection or extrusion in terms of energy consumption.

RIM technology having this advantage must satisfy the following conditions.

(1) Under normal conditions, each reaction mixture should be stable and not change over long periods of storage.

(2) It shall not solidify in the mixing head and be fully mixed.

(3) Solids should be produced quickly during injection in the mold.

(4) No additives shall interfere with the polymerization.

Historically, DCPD polymers for RIM processes have been prepared by ringopening metathesis polymerization (ROMP) with, for example, Group 6 or Group 8 carbene complex catalysts, as shown in Scheme 1 below.

Carbene complexes have been used to produce insitu phases in the process for economic reasons. Various promoters have been investigated and optimizations have been made to improve the efficiency of this process.

However, Wagner examined the DCPD polymerization process using ROMP catalyst. As shown in Scheme 2, Wagner showed polymerization in the first step by ROMP of 6-membered double bond, but in the second step by coordination polymerization of 5-membered ring double bond. Cross linking was confirmed (see KB Wagener, Macromolecules, 1996, 29, 786788).

Therefore, if only appropriate catalysts are developed, coordination polymerization using two types of double bonds present in DCPD will be possible, and new properties and structures of DCPD polymers are expected to be secured.

In the case of DCPD polymer obtained by the ROMP process, since a considerable amount of double bonds are present, it is likely to be decomposed by UV irradiation, and thus additional steps or measures are required to prevent them. In other words, a hydrogenation process is required, which is expensive and has a high process risk due to the use of highly reactive hydrogen. In addition, the catalyst precursor used in the ROMP process (e.g., MCl ₆ or MOCl ₄ , where M = Mo or W) is an ionic material that does not dissolve well in DCPD or non-polar organic solvents, which are non-polar, resulting in high dispersibility. Can't. Therefore, in order to prevent this phenomenon, a polar solvent such as lower alcohols and phenol is used. However, these compounds could potentially act as catalyst poisons and have a negative effect.

Therefore, in order to increase the efficiency of the process, if a high solubility catalyst is developed in an organic solvent including monomer DCPD, it is expected that it is possible to eliminate the use of a polar solvent, which is a potential catalyst poison.

In addition, one embodiment of the present invention is to provide a novel polymerization catalyst to obtain a DCPD polymer by coordination polymerization.

In addition, one embodiment of the present invention is to provide a new catalyst having a high solubility in a non-polar solvent.

In addition, one embodiment of the present invention is to provide a transition metal compound having high solubility in a non-polar solvent and enable coordination polymerization of DCPD.

One embodiment of the present invention is to provide a DCPD polymer that is stable against UV, and does not require additional hydrogenation process, such as DCPD polymer obtained by ROMP, and has a long shelf life.

In one embodiment of the present invention, at least one Group 10 transition metal compound selected from the compounds represented by Formula 1, Formula 2, or Formula 3; A polymerization catalyst containing an organoaluminumoxy compound is provided.

Wherein R is an alkyl or aryl group having 1 to 8 carbon atoms, R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or a combination thereof including a hetero atom (N or O), and L is pyridine or MR ' ₃ (wherein M is N, P or As, R 'is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms), and R ₃ is an alkyl group having 1 to 4 carbon atoms or 6 to 8 carbon atoms It is an aryl group.

Wherein R and R ³ are the same as defined in Chemical Formula 1, and n is an integer of 1 to 2.

Wherein R is as defined in Formula 1, R ¹ and R ² are the same as or different from each other as defined in R ¹ of Formula 1, and L and R ³ are as defined in Formula 1.

In the polymerization catalyst according to one embodiment of the present invention, the organoaluminumoxy compound (MAO compound may be modified methylaluminoxane or pure methylaluminoxane).

The polymerization catalyst according to one embodiment of the present invention may be for preparing a polymer of dicyclopentadiene.

Another embodiment of the present invention provides a Group 10 transition metal compound represented by Formula 1 below.

Formula 1

Wherein R is an alkyl or aryl group having 1 to 8 carbon atoms, R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or a combination thereof including a hetero atom (N or O), and L is pyridine or MR ' ₃ (wherein M is N, P or As, R 'is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms), and R ₃ is an alkyl group having 1 to 4 carbon atoms or 6 to 8 carbon atoms It is an aryl group.

Another embodiment of the present invention provides a Group 10 transition metal compound represented by Formula 2 below.

Formula 2

Wherein R and R ³ are the same as defined in Chemical Formula 1, and n is an integer of 1 to 2.

Another embodiment of the present invention provides a Group 10 transition metal compound represented by Formula 3 below.

Formula 3

Wherein R is as defined in Formula 1, R ¹ and R ² are the same as or different from each other as defined in R ¹ of Formula 1, and R ³ and L are as defined in Formula 1.

Another embodiment of the present invention provides a dicyclopentadiene polymer obtained by coordination polymerization of dicyclopentadiene in the presence of the polymerization catalyst described above.

In this case, the coordination polymerization may be performed by including a nonpolar solvent as an additive, or may be performed without including the solvent as an additive.

According to one embodiment of the present invention by providing a new Pd (II) complex and a polymerization catalyst comprising the same in high solubility in a non-polar solvent and applied to the preparation of DCPD coordination polymer, unlike the conventional PDPD polymer using ROMP polymerization It eliminates the need for hydrogenation and eliminates the use of polar solvents, which are catalyst poisons, which are economical for longer shelf life and secure new properties of DCPD polymers. It is expected to be able.

Hereinafter, the DCPD polymer and the polymerization catalyst of the present invention will be described in detail.

In the above and the following description, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may be used to mean not only homopolymer but also copolymer. .

First, each component constituting the polymerization catalyst according to one embodiment of the present invention will be described.

(1) Group 10 transition metal compound

Group 10 transition metal compound among the components forming the polymerization catalyst of the present invention is a Group 10 compound having a β-ketoiminate or β-diketiminate ligand. Unlike most metal compounds, they have high solubility in nonpolar organic solvents such as hexane.

Group 10 transition metal compound according to an embodiment of the present invention may be a compound represented by the following formula (1) as an example.

Formula 1

Wherein R is an alkyl or aryl group having 1 to 8 carbon atoms, R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or a combination thereof including a hetero atom (N or O), and L is pyridine or MR ' ₃ (wherein M is N, P or As, R 'is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms), and R ₃ is an alkyl group having 1 to 4 carbon atoms or 6 to 8 carbon atoms It is an aryl group.

In Formula 1, examples of R include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1, -dimethylpropyl, 2,2-dimethylpropyl, 1,1, -diethylpropyl , 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, CF ₃ or phenyl etc. are mentioned.

In Formula 1, examples of R ¹ include (CH ₂ ) ₃ OCH ₃ , 2-methoxybenzyl, 2- (CH ₂ ) ₂ pyridine, 2- (CH ₂ ) pyridine, 2-methoxyphenyl, and the like.

In the formula (1), examples of L include pyridine, triphenylphosphine, triethylphosphine, and the like.

In addition, in Formula 1, examples of R ³ include an alkyl group such as methyl and ethyl, and an aryl group such as phenyl and toryl.

Group 10 transition metal compound according to another embodiment of the present invention may be a compound represented by the following formula (2) as an example.

Formula 2

Wherein R and R ³ are the same as defined in Chemical Formula 1, and n is an integer of 1 to 2.

In Formula 2, examples of R include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1, -dimethylpropyl, 2,2-dimethylpropyl, 1,1, -diethylpropyl , 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, CF ₃ or phenyl etc. are mentioned.

In addition, in Chemical Formula 2, examples of R ³ include alkyl groups such as methyl, ethyl, and propyl, and aryl groups such as phenyl and toryl.

Group 10 transition metal compound according to another embodiment of the present invention may be a compound represented by the following formula (3) as an example.

Formula 3

Wherein R is as defined in Formula 1, R ¹ and R ² are the same as or different from each other as defined in R ¹ of Formula 1, and L and R ³ are as defined in Formula 1.

In Formula 3, examples of R include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1, -dimethylpropyl, 2,2-dimethylpropyl, 1,1, -diethylpropyl , 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, CF ₃ or phenyl etc. are mentioned.

In Formula 3, R ¹ and R ² is the same as or different from one another, Methyl group, ethyl group, n-propyl, isopropyl, 2-methylpropyl, 1,1, -dimethylpropyl, 2,2-dimethylpropyl, 1,1, -diethylpropyl, 1-ethyl-1-methylpropyl, 1 , 1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, CF ₃ or phenyl and the like.

In the formula (3), examples of L include pyridine, triphenylphosphine, triethyl phosphine, and the like.

In addition, in Chemical Formula 3, an example of R ³ may be an alkyl group such as methyl, ethyl or propyl, or an aryl group such as phenyl or toryl.

Group 10 transition metal compounds having a β-ketoiminate ligand as shown in Formulas 1 to 2, as shown in the following Scheme 3, are commonly used as a starting material with β-ketoiminate ligands as appropriate starting materials and Can be obtained through the reaction.

On the other hand, the Group 10 transition metal compound having a beta-dikytiminate ligand as shown in the formula (3) is β- produced by deprotonation of the beta-dikytimine ligand as shown in the following Scheme 4, for example It can be obtained through the substitution reaction of the dichitimate ligand with the appropriate Pd (II) precursor complex.

(2) promoter

The polymerization catalyst according to an embodiment of the present invention may include the Group 10 transition metal compound as a main catalyst and an organoaluminumoxy compound as a promoter.

The organoaluminumoxy compound that can be used in one embodiment of the present invention may be a conventionally known aluminoxane, for example modified methylaluminoxane or pure methylaluminoxane.

The organoaluminumoxy compound used for the polymerization of the olefinic compound may be produced by, for example, the following method and is usually obtained as a solution in a hydrocarbon solvent;

(1) Trialkylaluminum or the like in a hydrocarbon medium suspension such as a compound containing adsorbed water or a salt containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and cerium chloride hydrate. Adding an organoaluminum compound to react adsorbed or crystalline water with the organoaluminum compound.

(2) A method of directly reacting water, ice or water vapor to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, tetrahydrofuran and the like.

(3) A method in which organic tin oxides such as dimethyl tin oxide and dibutyltin oxide are reacted with free aluminum compounds such as trialkylaluminum in a medium such as decane, benzene, or toluene.

Examples of the organoaluminum compound that can be used to prepare the organoaluminumoxy compound include trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and the like. n-alkylaluminum; Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, Tri-branched alkyl aluminum such as tri4-methylpentyl aluminum, tri2-methylhexyl aluminum, tri3-methylhexyl aluminum and tri2-ethylhexyl aluminum; Tricycloalkyl aluminum, such as tricyclohexyl aluminum and tricyclooctyl aluminum; Triaryl aluminum, such as triphenyl aluminum and tritolyl aluminum; Dialkyl aluminum hydrides such as diisopropyl aluminum hydride and diisobutyl aluminum hydride; Alkenyl aluminum, such as isoprenyl aluminum represented by the formula (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y and z are positive and z ≦ 2x); Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide and isobutyl aluminum isopropoxide; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide; Alkyl aluminum seski alkoxides, such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; Partially alkoxylated alkylaluminum having an average composition represented by the formula R ^a _2.5 Al (OR ^b ) _0.5 and the like; Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diiso Alkyl aluminum aryl oxides such as butyl aluminum (2,6-di-t-butyl-4-methylphenoxide) and isobutyl aluminum bis (2,6-di-t-butyl-4-methylphenoxide); Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride; Alkyl aluminum seski halides, such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide; Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; Dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; Other partially hydrogenated alkyl aluminum such as alkyl aluminum dihydride such as ethyl aluminum dihydride and propyl aluminum dihydride; Partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. Aluminoxanes prepared from trimethylaluminum are called methylaluminoxanes or MAO. In addition, modified MAO (modified MAO, MMAO) or pure MAO (pure MAO, PMAO) may be used.

The Group 10 transition metal compound and the organoaluminumoxy compound can be used in combination as a catalyst for polymerization.

The catalyst for polymerization may further contain an organoaluminum compound, an organoboron compound, or the like.

Such a catalyst for polymerization according to one embodiment of the present invention may be particularly useful for preparing a polymer of dicyclopentadiene, and is particularly useful for preparing a copolymer of dicyclopentadiene.

Specific examples of preparing the DCPD coordination polymer according to one embodiment of the present invention will be described in detail below.

In the preparation of the DCPD copolymer, the polymerization can be performed by including a non-polar solvent as an additive, unlike the ROMP process of DCPD, which requires a polar solvent. All of the above-described polymerization catalysts are soluble in non-polar solvents. This may be possible because of the high.

Examples of the nonpolar solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane and kerosene, cyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, and aromatic hydrocarbons such as benzene, toluene and xylene. And petroleum oils such as gasoline, kerosene and diesel.

Furthermore, according to one embodiment of the present invention, a DCPD polymer may be prepared without a separate solvent under the above-described polymerization catalyst.

In one embodiment of the present invention DCPD polymerization is carried out in the presence of the above-described polymerization catalyst, in particular the Group 10 transition metal compound is 0.01mmol to 2.5M, preferably 0.1mmol based on the concentration of the transition metal atoms in the polymerization system May be used in amounts of 25M.

In addition, the organoaluminumoxy compound may be preferably used in an amount such that the molar ratio of the Group 10 transition metal atom is 90 to 120 equivalents, preferably 1.2 ml to 1.5 ml.

The polymerization may be preferably performed at room temperature to 50 ° C in view of yield and activity per unit time.

Atmosphere during polymerization may be carried out in an inert gas atmosphere.

The molecular weight of the resulting DCPD polymer can be controlled by solvent, temperature, DCPD equivalent to catalyst, and the like.

On the other hand, DCPD may be preferable because the lower the content of moisture can increase the yield and increase the catalytic activity. Therefore, it may be desirable to use distilled DCPD.

An example of a process for preparing DCPD polymers is to first polymerize DCPD with a Group 10 transition metal compound and then mix DCPD with a cocatalyst in another vessel and then mix these two solutions, or first DCDC and 10th. And a method of mixing a group transition metal compound and adding a cocatalyst to the solution to polymerize.

The DCPD polymer thus obtained is a coordinating polymer, and unlike the DCPD polymer obtained by the ROMP process, there is no residual double bond present in the polymer chain. Accordingly, a polymer stable to UV may be obtained even without performing a hydrogenation process.

According to one embodiment of the present invention, the Group 10 transition metal compound has high solubility in a nonpolar solvent and an organoaluminumoxy compound is also obtained in a nonpolar solvent, so that a DCPD polymerization process using these as a polymerization catalyst is a catalyst poison in the final DCPD polymer. It is possible to improve the storage stability of the obtained DCPD polymer as it can be carried out without using a working polar solvent, and also because there is no residual double bond in the DCPD polymer as the polymer is obtained by a coordination polymerization mechanism other than ROMP. Therefore, UV stability can be improved.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

Preparation Example of Group 10 Transition Metal Compound

In the following Examples it will be described an example of preparing a Group 10 transition metal compound included in the polymerization catalyst of the present invention.

Examples 1 to 9: Synthesis of Pd (II) Complexes Having β-ketoiminate Ligands

Examples 1 to 9 are for preparing the Group 10 transition metal compound represented by Chemical Formulas 1 to 2, and may be represented by Scheme 3 when the manufacturing process is schematically illustrated.

Scheme 3

Example 1 Pd (CH ₃ C (O) CHC (NCH ₂ CH ₂ CH ₂ OCH ₃ ) CH ₃ ) (PPh ₃ Me Synthesis (Compound 1b)

CH ₃ C (O) CHC (NHCH ₂ CH ₂ CH ₂ OCH ₃ ) CH ₃ Ligand (0.21 g, 1 mmol) was dissolved in 20 ml of THF, and this solution was mixed with distilled THF (30 mL) and Tl (OC). ₂ H ₅ ) (0.3 g, 1.2 mmol) was added dropwise. The resulting solution was stirred at room temperature for 1 hour and then the solvent was dried in vacuo. Then 30 ml of THF were added and [Pd (PPh ₃ ) MeCl] ₂ (0.51 g, 0.6 mmol, in 70 ml of THF) was added dropwise. After that, the mixture was stirred for 8 hours at room temperature, the mixture was filtered through celite on frit in a Schlenk flask and the solvent was vacuum dried. The product was washed with distilled hexanes and extracted with methylene glolide. The solvent was dried in vacuo to give a yellow solid (0.29 g, yield 52%, compound represented by compound 1b in Scheme 3).

¹ HNMR (199.976 MHz, CDCl ₃ ): 7.717.28 (m, 15H, P Ph ₃ ), 4.72 (s, 1H, C (O) C H = C (N)), 3.61 (m, 2H, N CH ₂ CH ₂ CH ₂ OCH ₃ ), 3.44 (t, 2H, J = 12.4 Hz, NCH ₂ CH ₂ CH ₂ OCH ₃ ), 3.41 (s, 3H, NCH ₂ CH ₂ CH ₂ OC H ₃ ), 2.023 (s , 3H, C (N) C H ₃ ), 1.92 (m, 2H, NCH ₂ C H ₂ CH ₂ OCH ₃ ), 1.55 (s, 3H, C H ₃ C (O)), 0.11 (d, J = 3.4 Hz, 3H, C H ₃ );

³¹ PNMR (162.027 MHz, CDCl ₃ ): 43.76; Anal. Calcd. For C ₂₈ H ₃₁ NO ₂ PPd: C, 61.04; H, 5.67; N, 2.54; Found C, 61.32; H, 6.00; N, 2.25.

Molecular weight: 550.95 g / mol

Example 2: Pd (CH ₃ C (O) CHC (NCH ₂ C ₆ H ₄ OCH ₃ ) CH ₃ ) (PPh ₃ Me Synthesis (Compound 4b)

Prepared in the same manner as in Example 1, except that CH ₃ C (O) CHC (NHCH ₂ CH ₂ CH ₂ OCH ₃ ) CH ₃ ligand (0.21 g, 1 mmol) instead of CH ₃ C (O) CHC (NHCH ₂ C ₆ H ₄ OCH ₃ ) CH ₃ (0.22 g, 1 mmol) was finally used to obtain a yellow solid (0.46 g, yield: 75%, compound represented by compound 4b in Scheme 3).

¹ HNMR (199.976 MHz, CDCl ₃ ): 7.627.17 (m, 17H), 7.00 (t, 1H, J = 7.4 Hz), 6.81 (d, 1H, J = 8.6 Hz) (P Ph ₃ and CH ₂ C) ₆ H ₄ OCH ₃ ), 4.88 (s, 1H, C (O) C H = C (N)), 4.77 (d, 2H, J = 8.6 Hz, NC H ₂ C ₆ H ₄ OCH ₃ ), 3.82 ( s, 3H, CH ₂ C ₆ H ₄ OC H ₃ ) _, 1.89 (s, 3H, C (N) C H ₃ ), 1.61 (s, 3H, C H ₃ C (O)), 0.08 (d, J = 3.6 Hz, 3H, C H ₃ ); ¹³ CNMR (50.289 MHz, CDCl ₃ ): 178.00 (CH ₃ C (O) CH), 166.68 (CH = C (N) CH ₃ ), 155.98, 134.88, 134.76, 131.44, 130.97, 129.94, 129.91, 127.84, 127.74 , 127.07, 126.61, 120.35, 109.23 (P Ph ₃ and CH ₂ C ₆ H ₄ OCH ₃ ), 97.56 (C (O) C H = C (N)), 55.15 ( C H ₂ C ₆ H ₄ OCH ₃ ) , 49.02 (CH ₂ C ₆ H ₄ O C H ₃ ), 26.38 ( C H ₃ C (O) CH), 23.28 (CH = C (N) C H ₃ ), 0.78 ( C H ₃ );

³¹ PNMR (162.027 MHz, CDCl ₃ ): 44.31; Anal. Calcd. For C ₃₂ H ₃₁ NO ₂ PPd: C, 64.17; H, 5. 22; N, 2.34; Found C, 63.84; H, 5.59; N, 2.10.

Molecular weight: 598.99 g / mol

Example 3: Pd (CH ₃ C (O) CHC ((2NCH ₂ CH ₂ ) Pyridine) CH ₃ ) (PPh ₃ Me Synthesis (6b)

Prepared in the same manner as in Example 1, except that CH ₃ C (O) CHC (NHCH ₂ CH ₂ CH ₂ OCH ₃ ) CH ₃ ligand (0.21 g, 1 mmol) instead of CH ₃ C (O) CHC (( 2NHCH ₂ CH ₂ ) Pyridine) CH ₃ (0.19 g, 1 mmol) was finally used to obtain a yellow solid (0.25 g, yield: 43%, compound represented by compound 6b in Scheme 3).

¹ HNMR (199.976 MHz, CDCl ₃ ): 8.54 (d, 1H, J = 6.2 Hz), 7.687.05 (m, 18H) (P Ph ₃ and Py ), 4.72 (s, 1H, C (O) C H = C (N)), 3.88 (m, 2H, NC H ₂ C H ₂ Py), 3.10 (dt, 2H, J = 7.8,7.4 Hz, NCH ₂ C H ₂ Py), 1.98 (s, 3H, C (N) C H ₃ ), 1.85 (s, 3H, C H ₃ C (O)), 0.21 (d, J = 3.2 Hz, 3H, C H ₃ ); ¹³ CNMR (50.289 MHz, CDCl ₃ ): 179.00 (CH ₃ C (O) CH), 156.68 (CH = C (N) CH ₃ ), 152.98, 135.05, 134.98, 134.87, 134.76, 130.05, 128.42, 128.11, 127.95 , 127.85, 127.07, 126.61, 121.45, 109.53 (P Ph ₃ and Py), 97.56 (C (O) C H = C (N)), 40.74 (N C H ₂ CH ₂ ), 31.88 (NCH ₂ C H ₂ ), 23.84 ( C H ₃ C (O) CH), 16.82 (CH = C (N) C H ₃ ), 0.819 ( C H ₃ );

³¹ PNMR (162.027 MHz, CDCl ₃ ): 44.77; Anal. Calcd. For C ₃₁ H ₃₃ N ₂ OPPd: C, 63.43; H, 5.71; N, 4.77; Found C, 63.56; H, 5.95; N, 4.86.

Molecular Weight: 587.00 g / mol

Example 4 Pd (PhC (O) CHC ((2NCH) ₂ CH ₂ ) Pyridine) Ph) (PPh ₃ Me Synthesis (12b)

Prepared in the same manner as in Example 1, except that CH ₃ C (O) CHC (NHCH ₂ CH ₂ CH ₂ OCH ₃ ) CH ₃ ligand (0.21 g, 1 mmol) instead of PhC (O) CHC ((2NHCH ₂ CH ₂ ) Pyridine) Ph (0.31 g, 1 mmol) was used to finally obtain a yellow solid (0.58 g, yield: 81%, compound represented by 12b in Scheme 3).

¹ HNMR (199.976 MHz, CDCl ₃ ): 8.42 (d, 1H, J = 6.2 Hz), 7.776.99 (m, 28H) (P Ph ₃ , Ph and Py ), 5.37 (s, 1H, C (O) C H = C (N)), 3.80 (m, 2H, NC H ₂ CH ₂ Py), 3.16 (t, 2H, J = 15.6 Hz, NCH ₂ C H ₂ Py), 0.35 (d, J = 3.0 Hz , 3H, C H ₃ ); ¹³ CNMR (50.289 MHz, CDCl ₃ ): 172.54 (Ph C (O) CH), 160.15 (CH = C (N) Ph), 142.36, 142.69, 142.64, 140.88, 136.09, 135.04, 134.93, 131.87, 131.40, 130.29 , 130.27, 128.76, 128.48, 128.38, 128.27, 127.68, 127.41, 127.21, 127.16, 123.64, 121.17 (P Ph ₃ , Ph and Py ), 96.52 (C (O) C H = C (N)), 52.04 (N C H ₂ CH ₂ ), 42.88 (NCH ₂ C H ₂ ), 0.92 ( C H ₃ );

³¹ PNMR (162.027 MHz, CDCl ₃ ): 43.73; Anal. Calcd. For C ₄₁ H ₃₇ N ₂ OPPd: C, 69.25; H, 5. 24; N, 3.94; Found C, 69.33; H, 5. 16; N, 3.74.

Molecular weight: 711.14 g / mol

Example 5: Pd (CF ₃ C (O) CHC (NCH ₂ CH ₂ CH ₂ OCH ₃ CF ₃ ) (PPh ₃ Me Synthesis (13b)

Prepared in the same manner as in Example 1 except for CH ₃ C (O) CHC (NHCH ₂ CH ₂ CH ₂ OCH ₃ ) CH ₃ ligand (0.21 g, 1 mmol) instead of CF ₃ C (O) CHC (NHCH ₂ CH ₂ CH ₂ OCH ₃ ) CF ₃ (0.26 g, 1 mmol) was used to finally give a yellow solid (0.56 g, yield: 85%, compound represented by 13b in Scheme 3).

¹ HNMR (199.976 MHz, CDCl ₃ ): 7.707.36 (m, 15H, P Ph ₃ ), 5.581 (s, 1H, C (O) C H = C (N)), 3.811 (br, 2H, NC H ₂ CH ₂ ), 3.438 (t, 2H, J = 8.6 Hz, CH ₂ C H ₂ OMe), 3.320 (s, 3H, OC H ₃ ), 2.127 (m, 2H, NCH ₂ C H ₂ CH ₂ ), 0.278 (d, 3H, J = 2.8 Hz, C H ₃ ); ¹³ CNMR (50.289 MHz, CDCl ₃ ): 165.99 (CF ₃ C (O) CH), 154.90 (CH = C (N) CF ₃ ), 135.05 to 128.05 (P Ph ₃ ), 120.75, 117.90 ( C F ₃ ) , 87.35 (C (O) C H = C (N)), 70.27 (N C H ₂ CH ₂ ), 58.56 (CH ₂ C H ₂ OMe), 49.18 (O C H ₃ ), 34.29 (NCH ₂ C H ₂ CH ₂ ), 0.14 ( C H ₃ );

³¹ PNMR (162.027 MHz, CDCl ₃ ): 42.99; Anal. Calcd. For C ₂₈ H ₂₈ F ₆ NO ₂ PPd: C, 50.81; H, 4. 26; N, 2.12; Found: C, 51.23; H, 4. 46; N, 1.65.

Molecular weight: 661.91 g / mol

Example 6: Pd (CH ₃ C (O) CHC ((2NCH ₂ CH ₂ ) Pyridine) CH ₃ Me Synthesis (6c)

MeC (O) CHC ((2NHCH ₂ CH ₂ ) pyridine) Me (0.248 g, 1.215 mmol) ligand was dissolved in 20 ml of THF and the solution was distilled THF (30 mL) and Tl (OC ₂ H ₅ ) (0.3 g, 1.2 mmol) was added dropwise to the mixture. The resulting solution was stirred at room temperature for 1 hour and then the solvent was dried in vacuo. 30 ml of THF was added and Pd (NH ₂ CH ₂ C ₆ H ₅ ) ₂ MeCl (0.446 g, 1.203 mmol, in 70 ml of THF) was added dropwise. After stirring for 8 hours at room temperature, the mixture was filtered through celite on frit in a Schlenk flask and the solvent was dried in vacuo. The product was washed with distilled hexanes and extracted with methylene chloride. The solvent was dried in vacuo to give a final solid (0.21 g, yield: 52%, 6c compound in Scheme 3).

¹ HNMR (199.976 MHz, CDCl ₃ ): 8.53 (d, 1H, J = 2.6 Hz), 7.71 (dt, 1H, J = 0.8,8.6 Hz), 7.327.27 (m, 1H), 7.167.12 (dt , 1H, J = 0.6,7.4Hz) ( Py ), (s, 1H, C (O) C H = C (N)), 3.29 (br, 4H, NC H ₂ C H ₂ Py), 1.94 (s , 3H, C (N) C H ₃ ), 1.82 (s, 3H, C H ₃ C (O)), 0.62 (s, 3H, C H ₃ );

¹³ CNMR (50.289 MHz, CDCl ₃ ): 175.78 (CH ₃ C (O) CH), 163.83 (CH = C (N) CH ₃ ), 161.65, 153.22, 137.92, 124.17, 122.95 ( Py ), 98.04 (C ( O) C H = C (N)), 46.58 (N C H ₂ CH ₂ ), 41.75 (NCH ₂ C H ₂ ), 26.67 ( C H ₃ C (O) CH), 22.43 (CH = C (N) C H ₃ ), 3.74 ( C H ₃ ); Anal. Calcd. For C ₁₃ H ₁₈ N ₂ OPd: C, 48.09; H, 5.59; N, 8.63. Found: C, 48.24; H, 5. 37; N, 8.65.

Molecular weight: 324.71 g / mol

Example 7 Pd (PhC (O) CHC ((2NCH) ₂ CH ₂ ) Pyridine) Ph) Me Synthesis (12c)

Prepared in the same manner as in Example 6, except that PhC (O) CHC ((2NHCH ₂ CH ₂ ) Pyridine instead of MeC (O) CHC ((2NHCH ₂ CH ₂ ) pyridine) Me (0.248 g, 1.215 mmol) ligand ) Ph (0.41 g, 1.215 mmol) was used to finally give a solid (0.19 g, lactation: 49%, 12c compound in Scheme 3).

¹ HNMR (199.976 MHz, CDCl ₃ ): 8.66 (d, 1H, J = 5.4 Hz), 7.83 (m 2H), 7.73 (t 1H, J = 7.6 Hz), 7.377.20 (m, 10H) ( Ph ) , 5.52 (s, 1H, C (O) C H = C (N)), 3.21 (br, 4H, NC H ₂ C H ₂ Py), 0.87 (s, 3H, C H ₃ );

¹³ CNMR (50.289 MHz, CDCl ₃ ): 171.78 (Ph C (O) CH), 162.18 (CH = C (N) Ph), 153.47, 141.84, 140.99, 138.05, 129.03, 128.54, 128.34, 128.03, 127.19, 127.09 , 124.31, 123.06 ( Ph ), 96.40 (C (O) C H = C (N)), 49.16 (N C H ₂ CH ₂ ), 42.28 ((NCH ₂ C H ₂ ), 5.28 ( C H ₃ ); Anal.Calcd.For C ₂₃ H ₂₂ N ₂ OPd: C, 61.55; H, 4.94; N, 6.24.Found: C, 61.89; H, 5.48; N, 6.31.

Molecular Weight: 448.85 g / mol

Example 8: Pd (CH ₃ C (O) CHC ((2NCH ₂ ) Pyridine) CH ₃ Me Synthesis (14c)

Prepared in the same manner as in Example 6, except that CH ₃ C (O) CHC ((2NHCH ₂ ) Pyridine in place of MeC (O) CHC ((2NHCH ₂ CH ₂ ) pyridine) Me (0.248g, 1.215 mmol) ligand ) CH ₃ (0.23 g, 1.215 mmol) was used to obtain a solid (0.29 g, yield: 61%, 14c compound in Scheme 3).

¹ HNMR (199.976 MHz, CDCl ₃ ): 8.48 (d, 1H, J = 5.8 Hz), 7.76 (dt, 1H, J = 0.8,8.6 Hz), 7.389∼7.190 (m, 2H) ( Py ), 4.95 ( s, 1H, C (O) C H = C (N)), 4.89 (s, 2H, NC H ₂ ), 2.04 (s, 3H, C (N) C H ₃ ), 1.95 (s, 3H, C H ₃ C (O)), 0.64 (s, 3H, C H ₃ );

¹³ CNMR (50.289 MHz, CDCl ₃ ): 176.72 (CH ₃ C (O) CH), 165.41 (CH = C (N) CH ₃ ), 162.05, 149.42, 136.83, 123.15, 121.48 ( Py ), 98.52 (C ( O) C H = C (N)), 58.98 (N C H ₂ ), 27.00 ( C H ₃ C (O) CH), 20.80 (CH = C (N) C H ₃ ), 1.54 ( C H ₃ ) ; Anal. Calcd. For C ₁₂ H ₁₆ N ₂ OPd: C, 46.39; H, 5. 19; N, 9.02; Found C, 46.50; H, 5.53; N, 8.61.

Molecular weight: 310.69 g / mol

Example 9: Pd (PhC (O) CHC ((2NCH) ₂ ) Pyridine) Ph) Me Synthesis (15c)

Prepared in the same manner as in Example 6, except that PhC (O) CHC ((2NHCH ₂ ) Pyridine) Ph instead of MeC (O) CHC ((2NHCH ₂ CH ₂ ) pyridine) Me (0.248g, 1.215 mmol) ligand (0.38 g, 1.215 mmol) was used to finally give a solid (0.22 g, yield: 55%, 15c compound in Scheme 3).

¹ HNMR (199.976 MHz, CDCl ₃ ): 8.31 (dt, 1H, J = 6.4 Hz), 7.86 (dd 1H, J = 0.8,4.8 Hz), 7.81 (dd 1H, J = 0.8, 4.8 Hz), 7.387. 10 (m, 10H), 7.16 (t, 1H, J = 7.8 Hz) ( Ph and Py ), 5.58 (s, 1H, C (O) C H = C (N)), 4.81 (s, 2H, NC H ₂ ), 0.88 (s, 3H, C H ₃ );

¹³ CNMR (50.289 MHz, CDCl ₃ ): 175.06 (Ph C (O) CH), 164.29 (CH = C (N) Ph), 162.71, 161.16, 150.05, 148.97, 141.17, 138.95, 137.70, 136.72, 130.03, 128.94 , 128.43, 127.99, 127.20, 125.41, 124.09, 120.78 ( Ph and Py ), 96.40 (C (O) C H = C (N)), 44.28 (N C H ₂ ), 5.28 ( C H ₃ ); Anal. Calcd. For C ₂₂ H ₂₀ N ₂ OPd: C, 60.77; H, 4. 64; N, 6.44; Found C, 60.43; H, 4. 60; N, 6.34.

Molecular weight: 434.83 g / mol

<Examples 10-17: Synthesis of Pd (II) complexes having β-diketiminate ligands>

Examples 10 to 17 are examples of preparing the compounds represented by Chemical Formula 3, and the reaction process is schematically illustrated in the following Scheme 4.

Scheme 4

Example 10: (Ph) ₂ nacnacPd (PPh ₃ Me Synthesis (16a)

(Ph) ₂ nacnacH (0.25 g, 1 mmol) was dissolved in 20 ml of dried hexanes and added dropwise into NaH (0.03 g, 1.2 mmol) in 30 ml hexanes. The resulting solution was then stirred for 4 hours at room temperature. The mixture was filtered through celite.

With continued stirring, [Pd (PPh ₃ ) MeCl] ₂ (0.51 g, 0.6 mmol) in 30 ml dry hexane was added dropwise at room temperature for 8 hours. The mixture was filtered through celite and the filtrate was concentrated by crystallization at 20 ° C. This was filtered to give yellow solids which were then dried in vacuo to give a pale yellow solid (0.58 g, yield: 87%, compound 16a in Scheme 4).

¹ HNMR (400.265 MHz, CDCl ₃ ): 7.703 (d, 1H, J = 4.8 Hz), 7.355-7.187 (m, 17H), 7.019 (m, 3H), 6.660 (t, 2H, J = 5.2 Hz), 6.299 (d, 2H, J = 3.2 Hz), 4.709 (s, 1H), 1.883 (s, 3H), 1.650 (s, 3H), 0.424 (d, 3H, J = 4.4 Hz);

¹³ CNMR (100.657 MHz, CDCl ₃ ): 179.456, 164.114, 151.485, 134.725, 134.603, 132.989, 132.034, 131.935, 131.821, 131.799, 129.903, 129.881, 128.448, 128.327, 128.092, 127.796, 127.690, 125.348, 123.460 96.580, 29.744, 26.772, 25.446, 2.083

³¹ PNMR (162.027 MHz, CDCl ₃ ): 41.317

Anal. Calcd. For C ₃₆ H ₃₅ N ₂ PPd: C, 68.30; H, 5.57; N, 4.43; Found C, 68.70; H, 5.77; N, 3.90

Molecular Weight: 633.07

Example 11: (dmp) ₂ nacnacPd (PPh ₃ Me synthesis (16b)

(dmp) ₂ nacnacH (0.31 g, 1 mmol) was dissolved in 20 ml of dry hexane. This solution was added dropwise into NaH (0.03 g, 1.2 mmol) in 30 ml hexanes. The resulting solution was then stirred for 4 hours at room temperature. The mixture was filtered through celite.

To this solution was added dropwise [20 [deg.] C, 0.6 mmol) [Pd (PPh ₃ ) MeCl] ₂ (0.51 g, 0.6 mmol) in 30 ml dry hexane for 8 hours at 20 ^° C. The mixture was filtered through celite and the filtrate was concentrated by crystallization at -20 ° C. This was filtered to give yellow solids which were then dried in vacuo to give a pale yellow solid (0.38 g, yield: 55%, compound 16b in Scheme 4).

¹ HNMR (400.265 MHz, CDCl ₃ ): 7.685 (t, 2H, J = 18.0 Hz), 7.533 (d, 2H, J = 8.0 Hz), 7.474 ~ 7.111 (m, 15H), 6.692 (t, 2H, J = 10.2 Hz), 4.813 (s, 1H), 2.276 (s, 6H), 2.034 (s, 6H), 1.686 (s, 3H), 1.638 (s, 3H), 0.814 (d, 3H, J = 4.4 Hz );

¹³ CNMR (100.657 MHz, CDCl ₃ ): 179.248, 166.314, 154.418, 134.725, 134.803, 132.975, 132.134, 131.635, 131.521, 131.799, 129.803, 129.781, 128.408, 128.327, 128.092, 127.896, 127.390, 126.348, 126.348. 94.390, 24.682, 24.194, 18.932, 18.786, 0.658

³¹ PNMR (162.027 MHz, CDCl ₃ ): 43.278

Anal. Calcd. For C ₄₀ H ₄₃ N ₂ PPd: C, 69.71; H, 6. 29; N, 4.06; Found C, 69.37; H, 5.83; N, 3.93

Molecular Weight: 689.18

Example 12: (Ph) ₂ nacnacPd (PEt ₃ Me synthesis (17a)

(Ph) ₂ nacnacH (0.25 g, 1 mmol) was dissolved in 20 ml of dry hexane. This solution was added dropwise into NaH (0.03 g, 1.2 mmol) in 30 ml hexanes. The resulting solution was then stirred for 4 hours at room temperature. The mixture was filtered through celite.

To this solution was added dropwise for 8 hours at room temperature with continuous stirring of [Pd (PEt ₃ ) MeCl] ₂ (0.33 g, 0.6 mmol) in 30 ml dry hexane. The mixture was filtered through celite and the filtrate was concentrated by crystallization at -20 ° C. This was filtered to give yellow solids which were then vacuum dried to give a pale yellow solid (0.41 g, yield: 83%, compound 17a in Scheme 4).

¹ HNMR (400.265 MHz, CDCl ₃ ): 7.261 (dd, 3H, J = 5.2 Hz), 7.204 (m, 2H), 7.086 (m, 2H), 6.895 (d, 2H,, J = 6.0 Hz), 4.648 (s, 1H), 1.799 (s, 3H), 1.770 (s, 3H), 1.242 (m, 6H), 0.934 (m, 9H), 0.401 (s, 3H);

¹³ CNMR (100.657 MHz, CDCl ₃ ): 156.715, 156.513, 132.246, 131.851, 128.796, 128.637, 127.326, 125.158, 123.422, 122.947, 96.430, 28.394, 26.657, 19.374, 17.902, 15.127, 13.314, 8.081, 1.105

³¹ PNMR (162.027 MHz, CDCl ₃ ): 24.007

Anal. Calcd. For C ₃₆ H ₃₅ N ₂ PPd: C, 58.95; H, 7.22; N, 5.73; Found C, 58.72; H, 7.61; N, 5.80

Molecular Weight: 488.16

Example 13: (dmp) ₂ nacnacPd (PEt ₃ Me Synthesis (17b)

(dmp) ₂ nacnacH (0.31 g, 1 mmol) was dissolved in 20 ml of dry hexane. This solution was added dropwise into NaH (0.03 g, 1.2 mmol) in 30 ml hexanes. The resulting solution was then stirred for 4 hours at room temperature. The mixture was filtered through celite.

To this solution was added dropwise [Pd (PEt ₃ ) MeCl] ₂ (0.33 g, 0.6 mmol) in 30 ml dry hexane at room temperature with stirring. The mixture was filtered through celite and the filtrate was concentrated by crystallization at -20 ° C. This was filtered to give yellow solids, which were then dried in vacuo to give a pale yellow solid (0.40 g, yield: 75%, 17b compound in Scheme 4).

¹ HNMR (400.265 MHz, CDCl ₃ ): 7.046 (d, 2H, J = 7.2 Hz), 7.010 (d, 2H, J = 7.2 Hz), 6.899 (t, 2H, J = 15.6 Hz), 4.724 (s, 1H), 2.328 (s, 6H), 2.220 (s, 6H), 1.560 (s, 3H), 1.460 (s, 3H), 0.942 (m, 6H), 0.850 (m, 9H), 0.621 (d, 3H) , J = 4.0 Hz);

¹³ CNMR (100.657 MHz, CDCl ₃ ): 150.795, 132.473, 132.246, 132.041, 127.796, 127.637, 127.326, 124.158, 123.422, 122.937, 97.180, 25.294, 23.657, 19.374, 18.912, 18.411, 14.197, 13.924, 8.481, 8.238, 2.382

³¹ PNMR (162.027 MHz, CDCl ₃ ): 22.402

Anal. Calcd. For C ₃₆ H ₃₅ N ₂ PPd: C, 61.70; H, 7.95; N, 5.14; Found C, 61.31; H, 7.77; N, 5.41

Molecular Weight: 544.22

Example 14: (Ph) ₂ nacnacPdPyMe Synthesis (18a)

(Ph) ₂ nacnacH (0.25 g, 1 mmol) was dissolved in 20 ml of dry hexane. This solution was added dropwise into NaH (0.03 g, 1.2 mmol) in 30 ml hexanes. The resulting solution was then stirred for 4 hours at room temperature. The mixture was filtered through celite.

 To this solution was added dropwise Pd (COD) MeCl (0.30 g, 1.1 mmol) (0.33 g, 1.2 mmol) in 30 ml dry hexane for 8 hours at room temperature with constant stirring. The mixture was filtered through celite and the filtrate was concentrated by crystallization at -20 ° C. This was filtered to give yellow solids which were then dried in vacuo to give a pale yellow solid (0.38 g, yield: 85%, compound 18a in Scheme 4).

¹ HNMR (400.265 MHz, CDCl ₃ ): 8.240 (dd, 2H, J = 6.0 Hz), 7.280 (m, 2H), 7.006 (m, 4H), 6.795 (m, 4H), 6.650 (m, 3H), 4.714 (s, 1H), 1.738 (s, 3H), 1.671 (s, 3H), 0.430 (s, 3H);

¹³ CNMR (100.657 MHz, CDCl ₃ ): 159.295, 159.075, 154.019, 153.026, 152.640, 135.599, 127.890, 127.784, 127.071, 125.540, 124.175, 123.326, 122.576, 94.588, 29.981, 26.464, 24.598, 3.602

Anal. Calcd. For C ₂₃ H ₂₅ N ₃ Pd: C, 61.40; H, 5.58; N, 9.34; Found C, 61.62; H, 5.01; N, 9.75

Molecular Weight: 499.11

Example 15: (dmp) ₂ nacnacPdPyMe Synthesis (18b)

(dmp) ₂ nacnacH (0.31 g, 1 mmol) was dissolved in 20 ml of dry hexane. This solution was added dropwise into NaH (0.03 g, 1.2 mmol) in 30 ml hexanes. The resulting solution was then stirred for 4 hours at room temperature. The mixture was filtered through celite.

To this solution a mixture of Pd (COD) MeCl (0.30 g, 1.1 mmol) and pyridine (0.15 g, 2 mmol) in 30 ml dry hexane was added dropwise at room temperature with stirring. The mixture was filtered through celite and the filtrate was concentrated by crystallization at -20 ° C. This was filtered to give yellow solids which were then vacuum dried to give a pale yellow solid (0.40 g, yield: 80%, 18b compound in Scheme 4).

¹ HNMR (400 MHz, CDCl ₃ ): {8.093 (dd 2H, J = 2, 6.4 Hz), 7.338 (t, 1H, J = 15.6 Hz), 6.770 (t, 2H, J = 14.0 Hz), pyridine} , (7.045 (d, 2H, J = 7.2 Hz), 6.892 (t, 1H, J = 15.2 Hz),, 6.595 (d, 2H, J = 7.4 Hz), 6.528 (t, 1H, J = 14.8 Hz) ; Phenyl}, 4.723 (s, 1H), 2.319 (s, 6H), 2.197 (s, 6H), 1.555 (s, 3H), 1.499 (s, 3H), 0.742 (s, 3H);

¹³ CNMR (100.657 MHz, CDCl ₃ ): 157.898, 157.428, 151.894, 151.136, 150.408, 135.331, 132.231, 131.200, 127.288, 127.121, 123.248, 123.392, 122.748, 93.290, 24.582, 23.194, 18.912, 18.737, 0.552

Anal. Calcd. For C ₂₇ H ₃₃ N ₃ Pd: C, 64.09; H, 6.57; N, 8.30; Found C, 64.26; H, 6. 33; N, 8.49.

Molecular Weight: 505.99

Example 16: (dep) ₂ nacnacPdPyMe Synthesis (18c)

(dep) ₂ nacnacH (0.36 g, 1 mmol) was dissolved in 20 ml of dry hexane. This solution was added dropwise into NaH (0.03 g, 1.2 mmol) in 30 ml hexanes. The resulting solution was then stirred for 4 hours at room temperature. The mixture was filtered through celite.

To this solution a mixture of Pd (COD) MeCl (0.30 g, 1.1 mmol) and pyridine (0.15 g, 2 mmol) in 30 ml dry hexane was added dropwise at room temperature with stirring. The mixture was filtered through celite and the filtrate was concentrated by crystallization at -20 ° C. This was filtered to give yellow solids which were then vacuum dried to give a pale yellow solid (0.44 g, yield: 80%, 18c compound in Scheme 4).

¹ HNMR (400.265 MHz, CDCl ₃ ): 8.010 (d, 2H, J = 5.6 Hz), 7.326 (t, 1H, J = 15.6 Hz), 7.102-7.009 (m, 4H), 6.751 (t, 2H, J = 13.2 Hz), 6.682 (m, 2H), 4.707 (s, 1H), 2.930 (m, 2H), 2.693 (m, 6H), 1.559 (s, 3H), 1.531 (s, 3H), 1.340 (t , 6H, J = 15.2 Hz), 1.185 (t, 6H, J = 14.8 Hz), 0.736 (s, 3H);

¹³ CNMR (100.657 MHz, CDCl ₃ ): 158.484, 158.257, 152.056, 150.358, 149.555, 137.297, 136.380, 135.417, 124.630, 124.251, 123.751, 123.562, 123.281, 93.414, 29.967, 25.221, 24.304, 24.107, 485. 13.457, 2.078

Anal. Calcd. For C ₃₁ H ₄₁ N ₃ Pd: C, 66.24; H, 7. 35; N, 7.48; Found C, 65.93; H, 7.04; N, 7.48

Molecular Weight: 561.23

Example 17: (tbp) ₂ nacnacPdPyMe Synthesis (18d)

((tbp) ₂ nacnacH (0.36 g, 1 mmol) was dissolved in 20 ml of dry hexane This solution was added dropwise into NaH (0.03 g, 1.2 mmol) in 30 ml hexane The resulting solution was then added for 4 hours at room temperature. The mixture was filtered through celite.

To this solution a mixture of Pd (COD) MeCl (0.30 g, 1.1 mmol) and pyridine (0.15 g, 2 mmol) in 30 ml dry hexane was added dropwise at room temperature with stirring. The mixture was filtered through celite and the filtrate was concentrated by crystallization at -20 ° C. This was filtered to give yellow solids which were then dried in vacuo to give a pale yellow solid (0.44 g, yield: 80%, 18d compound in Scheme 4).

¹ HNMR (400.265 MHz, CDCl ₃ ): 7.373 (q, 3H, J = 26.4 Hz), 7.116 (q, 3H, J = 23.2 Hz), 7.005 (t, 2H, J = 16.8 Hz), 6.850 (d, 1H, J = 9.6 Hz, 6.621 (t, 2H, J = 16.4 Hz), 6.380 (t, 1H, J = 16.4 Hz), 6.220 (d, 1H, J = 9.6 Hz), 4.647 (s, 1H) , 1.651 to 1.572 (m, 24H), 0.433 (s, 3H);

¹³ CNMR (100.657 MHz, CDCl ₃ ): 160.278, 159.952, 151.993, 150.704, 141.433, 141.380, 135.430, 131.306, 128.744, 126.894, 124.953, 124.969, 123.862, 123.634, 122.649, 94.602, 36.278, 32.435, 31.450, 31.450 29.752, 27.007, 24.961, 4.660

Anal. Calcd. For C ₃₁ H ₄₁ N ₃ Pd: C, 66.24; H, 7. 35; N, 7.48; Found C, 66.22; H, 7.09; N, 7.62.

Molecular Weight: 561.23

(Preparation of DCPD Polymer)

In the following embodiments, examples of preparing DCPD polymer using a polymerization catalyst using a Group 10 transition metal compound obtained through Examples 1 to 17 as a main catalyst and a cocatalyst are described.

In the following examples the backbone of the method of making the DCPD polymer is as follows; In a nitrogen gas atmosphere, one equivalent of the Group 10 transition metal compound and 300 equivalents of distilled DCPD were placed in a 10 mL or 20 mL vial containing a stir bar, and the vial was sealed with a rubber septum. To this, about 0.05 mL of toluene was added and the mixture was stirred gently to dissolve the solid. 100 equivalents of the organoaluminumoxy compound as a cocatalyst was added thereto, and the resultant solution was stirred until the viscosity was increased and stirring was stopped.

The reaction was quenched with acidic methanol (methanol / conc. HCl = 50/1 volume ratio) and the solid was filtered and then vacuum dried at 60 ° C for 12 hours.

Polymer Preparation Example 1 Effect of Reaction Time on DCPD Polymerization Using Group 10 Transition Metal Compounds of 4b and 15b

When the DCPD polymer was prepared under the same conditions as shown in Table 1 above, the yield and catalytic activity are shown in Table 1 below.

In this example, a 95% concentration of DCPD was used.

  division   DCPD (equivalent) Group 10 transition metal compound (equivalent)  Organic Aluminoxy Compound (Equivalent)  Reaction temperature (℃)  Response time (min)   yield(%)  Catalytic activity (kg / pd.molh) One 95% (300) 4b (1) MAO (100) 20 5 33 158.4 2 95% (300) 4b (1) MAO (100) 20 10 33 79.2 3 95% (300) 4b (1) MAO (100) 20 30 37 29.6 4 95% (300) 4b (1) MAO (100) 20 60 47 18.8 5 95% (300) 4b (1) MAO (100) 20 180 49 6.5 6 95% (300) 4b (1) MAO (100) 20 360 51 3.4 7 95% (300) 15b (1) MAO (100) 20 5 30 144.0 8 95% (300) 15b (1) MAO (100) 20 10 42 100.8 9 95% (300) 15b (1) MAO (100) 20 30 42 33.6 10 95% (300) 15b (1) MAO (100) 20 60 47 18.8 11 95% (300) 15b (1) MAO (100) 20 180 49 6.53 12 95% (300) 15b (1) MAO (100) 20 360 70 4.67

From the results in Table 1, it can be seen that under the same conditions, the longer the polymerization time, the higher the yield and the lower the catalytic activity.

Polymer Preparation Example 2 Effect of DCPD Concentration on DCPD Polymerization Using Group 10 Transition Metal Compounds Designated as 14b

When the DCPD polymer was prepared under the same conditions as shown in Table 2, the yield and catalytic activity are as shown in Table 2 below.

division DCPD (equivalent) Group 10 transition metal compound (1 equivalent) Organoaluminumoxy compound (equivalent) Response time (min) yield(%) Catalytic activity (kg / pd molh) One 95% (300) 14b MAO 100 30 23.7 94.8 2 100% (300) 14b MAO 100 30 77.1 308.4

Under the same conditions from Table 2, it can be seen that the higher the concentration of DCPD, that is, the more preferable the use of DCPD having a low moisture content in terms of yield or catalytic activity.

Polymer Preparation Example 3 Effect of Cyclopentadiene Content (Cp Content) in DCPD in DCPD Polymerization Using Group 10 Transition Metal Compounds Designated as 4b

When the DCPD polymer was prepared under the same conditions as shown in Table 3, the yield and catalytic activity are as shown in Table 3 below.

In this example, distilled DCPD was used.

division DCPD (equivalent) Group 10 transition metal compound (1 equivalent) Organoaluminumoxy compound (equivalent) Cp Content (%) menstruum Yield (%)   Catalytic activity (kg / pd.molh) One Distilled (300) 4b MAO (100) 0 toluene 97.6 70300 2 Distilled (300) 4b MAO (100) One toluene 96.3 46200 3 Distilled (300) 4b MAO (100) 5 toluene 95.95 27600 4 Distilled (300) 4b MAO (100) 7 toluene 94.1 12300 5 Distilled (300) 4b MAO (100) 10 toluene 88.85 8000 6 Distilled (300) 4b MAO (100) 12 toluene 62.25 3900 7 Distilled (300) 4b MAO (100) 15 toluene 56.5 2140 8 Distilled (300) 4b MAO (100) 17 toluene 45.65 822 9 Distilled (300) 4b MAO (100) 20 toluene 40.9 393

From the results in Table 3, it can be seen that the yield and catalytic activity decrease as the content of cyclopentadiene in dicyclopentadiene increases. Therefore, it can be seen that it is desirable to minimize the content of cyclopentadiene in dicyclopentadiene.

Polymer Preparation Example 4 Effect of Reaction Temperature and Cocatalyst (Organic Aluminum Oxy Compound or Organic Aluminum Compound) in DCPD Polymerization Using Group 10 Transition Metal Compounds of 16a and 16b

When the DCPD polymer was prepared under the same conditions as shown in Table 4, the yield and catalytic activity are as shown in Table 4 below.

division DCPD (equivalent) Group 10 transition metal compound (1 equivalent) Cocatalyst (equivalent) Reaction temperature (℃) yield(%) Catalytic activity (kg / pd.molh) One 100% (300) 16b MAO (100) 20 66 1.6 * 10 ³ 2 100% (300) 16b MAO (100) 50 72 1.7 * 10 ³ 11 Distilled (300) 16a AlEt ₃ (50) 20 5.3 4

From the results in Table 4, it can be seen that as the promoter, MAO, which is an organoaluminumoxy compound, exhibits significantly higher yield and catalytic activity than triethylaluminum, which is an organoaluminum compound. From this, it can be seen that the combination catalyst of the Group 10 transition metal compound and the organoaluminum oxy compound obtained from the above examples is an optimum for the preparation of the DCPD polymer.

In addition, under the same conditions, the higher the reaction temperature, the higher the yield and the catalytic activity. have.

Polymer Preparation Example 5 Effect of DCPD Content and Solvent Effect on DCPD Polymerization Using Group 10 Transition Metal Compounds Designated as 16a

When the DCPD polymer was prepared under the same conditions as shown in Table 5, the yield and catalytic activity were as shown in Table 5 below.

 division  DCPD (equivalent) Group 10 transition metal compound (1 equivalent) Organoaluminumoxy compound (equivalent) Reaction temperature (℃)   menstruum   yield(%)  Catalytic activity (kg / pd.molh) One Distilled (300) 16a MAO (100) 20 - 95.8 13000 2 Distilled (600) 16a MAO (100) 20 - 44.8 1100 3 Distilled (1200) 16a MAO (100) 20 - 67.9 2800 4 Distilled (300) 16a MAO (100) 20 Dichloromethane (1 ml) 50.3 4500 5 Distilled (600) 16a MAO (100) 20 Dichloromethane (1 ml) 64.2 6600 6 Distilled (1200) 16a MAO (100) 20 Dichloromethane (1 ml) 43.1 5400 7 Distilled (2400) 16a MAO (100) 20 Dichloromethane (1 ml) 18.9 130 8 Distilled (300) 16a MAO (100) 20 Toluene (1 ml) 40 1800 9 Distilled (600) 16a MAO (100) 20 Toluene (1 ml) 39.4 5400 10 Distilled (1200) 16a MAO (100) 20 Toluene (1 ml) 31.6 3000 11 Distilled (2400) 16a MAO (100) 20 Toluene (1 ml) 20.1 240

From the results of Table 5, it can be seen that under the same conditions, performing the polymerization reaction without solvent may be advantageous in terms of yield and catalytic activity, and also obtains proper yield and catalytic activity even in non-polar solvents of dichloromethane and toluene. Can be.

In addition, the effect of the DCPD content, when the polymerization without the solvent shows the best yield in DCPD 1200equiv., But 300equiv. In the case of exhibiting the best catalytic activity and performing in the presence of a nonpolar solvent, it can be seen that the yield and catalytic activity are generally reduced compared to the absence of the nonpolar solvent.

From these results, it can be seen that the Group 10 transition metal compound is preferably used in an amount of 0.1 mmol to 25 M based on the concentration of the transition metal atom in the polymerization reaction system.

1 is a schematic diagram illustrating an example of a process of applying DCPD to reaction injection molding.

Claims (9)

At least one Group 10 transition metal compound selected from the compounds represented by Formula 1, Formula 2, or Formula 3; And Polymerization catalyst containing an organoaluminumoxy compound. Formula 1

Wherein R is an alkyl or aryl group having 1 to 8 carbon atoms, R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or a combination thereof including a hetero atom (N or O), and L is pyridine or MR ' ₃ (wherein M is N, P or As, R 'is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms), and R ₃ is an alkyl group having 1 to 4 carbon atoms or 6 to 8 carbon atoms It is an aryl group. Formula 2

Wherein R and R ³ are the same as defined in Chemical Formula 1, and n is an integer of 1 to 2. Formula 3

Wherein R is as defined in Formula 1, R ¹ and R ² are the same as or different from each other as defined in R ¹ of Formula 1, and L and R ³ are as defined in Formula 1. The polymerization catalyst according to claim 1, wherein the organoaluminumoxy compound is methylaluminoxane (MAO). The polymerization catalyst according to claim 1, for producing a polymer of dicyclopentadiene. A group 10 transition metal compound represented by the following formula (1). Formula 1

Wherein R is an alkyl or aryl group having 1 to 8 carbon atoms, R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or a combination thereof including a hetero atom (N or O), and L is pyridine or MR ' ₃ (wherein M is N, P or As, R 'is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms), and R ₃ is an alkyl group having 1 to 4 carbon atoms or 6 to 8 carbon atoms It is an aryl group. Group 10 transition metal compound represented by the following formula (2). Formula 2

Wherein R and R ³ are the same as defined in Chemical Formula 1, and n is an integer of 1 to 2. A group 10 transition metal compound represented by the following formula (3). Formula 3

Wherein R is as defined in Formula 1, R ¹ and R ² are the same as or different from each other as defined in R ¹ of Formula 1, and L and R ³ are as defined in Formula 1. A dicyclopentadiene polymer obtained by coordination polymerization of dicyclopentadiene in the presence of the polymerization catalyst of claim 1. 8. The dicyclopentadiene polymer according to claim 7, wherein the coordination polymerization is performed by including a nonpolar solvent as an additive. 8. The dicyclopentadiene polymer according to claim 7, wherein the coordination polymerization is carried out without including a solvent as an additive.

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