KR102305814B1 - Ruthenium-Based Catalysts with Novel Ligands - Google Patents

Abstract

According to the present invention, the catalyst represented by Chemical Formulas 1 to 2 and the ruthenium-based catalyst having the novel ligand of the present invention have excellent potential, are stable at room temperature and high temperature, and can be activated with acid, so that it is advantageous for RIM molding and economically manufactured It relates to a manufacturing method.

Description

Ruthenium-Based Catalysts with Novel Ligands

The present invention relates to a ruthenium-based catalyst having a novel ligand. Specifically, it is to use a ruthenium-based catalyst having a novel ligand in the manufacture of PDCPD, which is stable at room temperature and high temperature and can be activated with an acid, thereby providing a favorable effect for RIM molding.

Olefin metathesis has proven to be a method for carbon-carbon bond formation and is used in organic synthesis and polymer chemistry in numerous applications. A number of catalyst systems have been developed over the past few decades that can initiate olefin metathesis reactions. However, ruthenium-based catalysts in olefin metathesis have attracted much attention because of their high reactivity. In addition, it has been widely used in olefin metathesis reactions because it is remarkably resistant to many organic functional groups such as alcohols, esters, aldehydes and ketones under mild conditions.

However, further research is needed to develop a catalyst capable of controlling the cis/trans selectivity in the olefin metathesis process. In addition, in order to facilitate the development of the catalyst, it is necessary to develop a catalyst that exhibits thermal stability and can maintain high activity in a polar protic solvent.

Specifically, in polymer chemistry, polydicyclopentadiene (PDCPD) exhibits high impact resistance, good chemical corrosion and thermal deformation temperature, and is used in the automotive industry to make body panels, bumpers and other truck, bus and tractor components and other dry materials. In order to form PDCPD, for efficient ring-opening metathesis polymerization (ROMP) reaction of DCPD (dicycopentadien), a catalyst and a monomer need to be stored together during a reaction injection molding (RIM) process. For this reason, proper mixing of the monomer and catalyst is required before polymerization is carried out to avoid gelation of the monomer.

In this regard, the latent behavior of the catalyst is very important to avoid room temperature polymerization. Rapid initiation polymerization cannot perform an appropriate pre-treatment process in the RIM process. To overcome these shortcomings, latent catalysts that exhibit slow onset rates or are inert at room temperature are needed.

Under this background, the present inventors have completed the present invention by identifying a ruthenium-based latent catalyst having a novel ligand as a result of earnest efforts to provide a stable, acid-activated, and advantageous effect for RIM molding at room temperature and high temperature.

One object of the present invention is to provide a catalyst represented by the following Chemical Formulas 1 to 2.

[Formula 1]

[Formula 2]

In the following formula (1),

Wherein X and Y are a ring compound or a heterocyclic compound.

Another object of the present invention is to provide a method for preparing a catalyst, which comprises the step of adding and stirring a compound represented by the following Chemical Formula 3 and a cyclic compound or a heterocyclic compound.

[Formula 3]

This will be described in detail as follows. Meanwhile, each description and embodiment disclosed in the present invention may be applied to each other description and embodiment. That is, all combinations of the various elements disclosed herein fall within the scope of the present invention. In addition, it cannot be considered that the scope of the present invention is limited by the specific descriptions described below.

A first aspect of the present invention for achieving the above object provides a catalyst represented by the following Chemical Formulas 1 to 2.

[Formula 1]

[Formula 2]

In the following formula (1),

Wherein X and Y are a ring compound or a heterocyclic compound.

A second aspect of the present invention for achieving the above object provides a method for preparing a catalyst, which comprises the step of adding and stirring a compound represented by the following Chemical Formula 3 and a cyclic compound or a heterocyclic compound.

[Formula 3]

.

.

Hereinafter, the present invention will be described in more detail.

As used herein, the term "ruthenium (Ru)" is an atomic number 44 element, a transition metal located in the center of the periodic table, and means one of the platinum group metals.

The "ring-opening polymerization" of the present invention is also called ROMP (ring-opening polymerization), and refers to a polymerization reaction in which a ring of a cyclic compound is opened to form a linear polymer.

The catalyst may be used for poly DCPD ring-opening reaction or COD ring-opening reaction (ROMP), but is not limited thereto.

In a method for preparing poly DCPD (PDCPD) by ring-opening polymerization (ring-opening reaction) of a DCPD monomer, the monomer DCPD may be subjected to ring-opening polymerization using the catalyst of Formula 1 to prepare poly DCPD.

The ring-opening reaction of the PDCPD can be represented by Scheme 9 below.

[Scheme 9]

The COD ring-opening reaction may be represented by the following Reaction Scheme 10.

[Scheme 10]

The term "DCPD" in the present invention means poly Dicyclopentadiene, a clear light yellow liquid with a clear odor at room temperature, co-produced in large quantities in steam cracking of naphtha and ethylene of gas oil. It can also be used in resins, especially unsaturated polyester resins and inks, adhesives and paints, for its main purpose. Poly (poly) DCPD can be prepared by ring-opening polymerization of a DCPD monomer. DCPD resin can be polymerized using a conventional tungsten-based catalyst, and the tungsten-based catalyst polymerization is performed under high temperature and high pressure and is polymerized by RIM molding. In order to apply a tungsten-based catalyst to DCPD resin, the required reaction pressure is very high, the reaction temperature is high, and the reaction rate is fast, so it is difficult to use DCPD resin with a general molding method. There is a need for a catalyst that can alleviate the reaction conditions for temperature and pressure to a general composite material molding process due to the same problem.

As used herein, the term “RIM” refers to DCPD polymerization using a catalyst. Catalytic polymerization is performed under high temperature and pressure, and polymerization is performed by RIM (Reaction Injection Molding) molding. RIM molding is a method of molding by mixing two components under a gas, injecting them into a mold, and polymerization in a short time. Usually, the pressure applied to RIM molding is about ^{200kgf/cm 2 .} When the reaction started, the temperature was 200°C, meaning that the injection, molding, cooling and demolding processes were completed within a working time of about 5 minutes. Therefore, RIM molding is generally applied to the type of complex structures. During the RIM process, catalyst and monomer need to be stored together, in which case proper mixing of monomer and catalyst before polymerization is carried out to avoid gelation of the monomer, and latent behavior of the catalyst, i.e., slow initiation rate to avoid room temperature polymerization Alternatively, a latent catalyst that is inert at room temperature is required.

, 또는

를 포함하는 것일 수 있으나, 이에 제한되지 않는다.X of Formula 1 of the first aspect described above is

, or

It may include, but is not limited thereto.

, 또는

를 포함하는 것일 수 있으나, 이에 제한되지 않는다.In Formula 2 of the above-described first aspect, Y is

, or

It may include, but is not limited thereto.

The catalyst of the present invention may be represented by the following Chemical Formulas 1-1 to 2-2, but is not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 2-1]

[Formula 2-2]

.

.

The catalyst of the first aspect described above includes a novel ligand coordinated with ruthenium, thereby providing a latent catalyst having a slow initiation rate or inert at room temperature. Therefore, it has excellent potential in the ROMP reaction, is stable at room temperature and high temperature, and can provide the effect of performing the necessary pretreatment process during RIM molding.

,

,

, 또는

를 포함하는 것일 수 있으나, 이에 제한되지 않는다.The cyclic compound or heterocyclic compound of the second aspect described above is

,

,

, or

It may include, but is not limited thereto.

The stirring may be carried out for an hour to 10 minutes to 1 hour. It may be preferable to proceed for 30 minutes, but it may be appropriately changed according to the reaction conditions and circumstances.

The heating may be performed at a temperature of 70° C. to 90° C. for 4 hours to 8 hours. Specifically, it may be preferable to heat at 80° C. for 6 hours, but may be appropriately changed according to reaction conditions and circumstances.

In a specific embodiment, it was confirmed that the ruthenium-based catalyst including the novel ligand has excellent stability, unlike the conventional catalyst, to provide a latent catalyst inactive at a slow initiation rate or room temperature.

The ruthenium-based catalyst having a novel ligand of the present invention has excellent potential, is stable at room temperature and high temperature, and can be activated with an acid, thereby providing an advantageous effect and economical manufacturing method for two-component RIM molding.

1 is a graph comparing the reaction rates of the catalysts prepared in Preparation Examples 2-1 to 2-4 of the present invention and the conventional catalyst.
2 is a comparative graph of measuring time and temperature during the ROMP reaction of DCPD using the catalysts prepared in Preparation Examples 2-1 to 2-4 and the existing catalyst (Ref 1) of the present invention.
3 is a TGA comparison graph of the PDCPD prepared using the catalyst prepared in Preparation Examples 2-1 to 2-3 of the present invention and the conventional catalyst (Ref 1).
^{4 is a 1} H NMR comparison graph measured during the ROMP reaction of COD prepared using the catalyst prepared in Preparation Examples 2-1 to 2-4 and the existing catalyst (Ref) of the present invention.

Hereinafter, the present invention will be described in more detail through examples. These Examples are for explaining the present invention in more detail, and the scope of the present invention is not limited by these Examples.

Preparation Example 1: Preparation of a novel ligand

Preparation 1-1: Preparation of novel ligand 1-1

A novel ligand 1-1 was prepared as shown in Scheme 1 below.

Specifically, in a solution of 2,2-dimethyl-4-pentenal (2,2-Dimethyl-4-pentenal) (0.250 g, 2.20 mmol), 2- (2-ethylamine) pyridine (2- (Pyridine-2- yl)ethan-1-amine) (0.272 g, 2.20 mmol) was added at room temperature (about 20 to 25° C.) and in a nitrogen atmosphere to prepare a mixture. The mixture was heated to 75° C. for 12 h. After the heated mixture was cooled to room temperature, the reaction mixture was concentrated under reduced pressure to remove the solvent, and the resulting concentrate was dried under high vacuum to obtain a pale yellow liquid (yield = 0.442 g 98%).

[Scheme 1]

Preparation 1-2: Preparation of novel ligand 1-2

A novel ligand 1-2 was prepared as shown in Scheme 2 below.

Specifically, in a solution containing 2,2-dimethyl-4-pentenal (0.250 g, 2.20 mmol) in toluene at room temperature (about 20 to 25° C.) and nitrogen atmosphere. 3-(2-aminoethyl)pyridine 3-(2-aminoethyl)pyridine) (0.272 g, 2.20 mmol) was added to prepare a mixture. The mixture was heated to 75° C. for 12 h. After cooling the heated mixture to room temperature, the reaction mixture was concentrated under reduced pressure to remove the solvent, and the resulting concentrate was dried under high vacuum to obtain a pale yellow liquid (yield = 0.432 g, 96%).

[Scheme 2]

Preparation Example 1-3: Preparation of Novel Ligand 1-3

Novel ligands 1-3 were prepared as shown in Scheme 3 below.

Specifically, in a solution containing 2,2-dimethyl-4-pentenal (0.260 g, 2.31 mmol) in toluene at room temperature (about 20 to 25° C.) and nitrogen atmosphere. 4- (2-Aminoethyl) pyridine (4- (2-Aminoethyl) pyridine) (0.283 g, 2.31 mmol) was added to prepare a mixture. The mixture was heated to 75° C. for 12 h. After the heated mixture was cooled to room temperature, the reaction mixture was concentrated under reduced pressure to remove the solvent, and the resulting concentrate was dried under high vacuum to obtain a pale yellow liquid (yield = 0.452 g, 96%).

[Scheme 3]

Preparation Example 1-4: Preparation of Novel Ligand 1-4

Novel ligands 1-4 were prepared as shown in Scheme 4 below.

)을 첨가하였다. 실온(약 20 내지 25℃) 및 질소대기중에 CH₂Cl₂중의 2,3-디하이드로-1H-인덴-2-아민(2,3-dihydro-1H-inden-2-amine)(0.594 g, 4.40 mmol)첨가하여 혼합물을 제조하였다. 혼합물을 12시간 동안 75℃로 가열하였다. 가열된 혼합물을 실온으로 냉각한 후, 반응 혼합물을 감압하에 용매를 제거한 후, 농축시키고, 생성된 농축액을 고진공하에 건조시켜 담황색 액체를 수득하였다(수율= 0.860g, 86%).Specifically, in a solution of 2,2-dimethyl-4-pentenal (2,2-Dimethyl-4-pentenal) (0.500 g, 4.40 mmol) CH ₂ Cl ₂ (0.75 g, 4.0

) was added. 2,3-dihydro-1H-inden-2-amine (0.594 g) in _{CH 2} Cl ₂ at room temperature (about 20-25° C.) and nitrogen atmosphere 4.40 mmol) was added to prepare a mixture. The mixture was heated to 75° C. for 12 h. After cooling the heated mixture to room temperature, the reaction mixture was concentrated under reduced pressure to remove the solvent, and the resulting concentrate was dried under high vacuum to obtain a pale yellow liquid (yield = 0.860 g, 86%).

[Scheme 4]

Preparation Example 2: Preparation of a ruthenium-based catalyst having a novel ligand

Preparation Example 2-1: Preparation of ruthenium-based catalyst 2-1

A ruthenium-based catalyst 2-1 was prepared as shown in Scheme 5 below.

Specifically, a solution of Formula 3 (0.200 g, 2.70 mmol) was added to a solution containing the novel ligand (0.089 g, 0.410 mmol) prepared in Preparation Example 1-1 in _{CH 2} Cl _{2 (2.50 mL), and} Stirred for 30 minutes. After stirring, the color of the mixture changed from green to light brown, and the solvent was removed under reduced pressure to give a light brown solid. The light brown solid was dissolved in 0.50 ml benzene, and 20 ml of pentane was added to obtain a yellow solid, which was filtered and washed with pentane (yield=0.120 g, 64%).

[Scheme 5]

Preparation Example 2-2: Preparation of ruthenium-based catalyst 2-2

A ruthenium-based catalyst 2-2 was prepared as shown in Scheme 6 below.

Specifically, a solution of Formula 3 (0.100 g, 0.137 mmol) was added to a solution containing the novel ligand (0.044 g, 0.206 mmol) prepared in Preparation Example 1-2 in _{CH 2} Cl _{2 (2.50 mL), and} Stirred for 30 minutes. After stirring, the color of the mixture changed from dark green to light green, and the solvent was removed under reduced pressure to give a light brown solid. The light brown solid was dissolved in 0.50 ml benzene, and 20 ml of pentane was added to obtain a yellow solid, which was filtered and washed with pentane (yield=0.082 g, 88%).

[Scheme 6]

Preparation 2-3: Preparation of ruthenium-based catalyst 2-3

A ruthenium-based catalyst 2-3 was prepared as shown in Scheme 7 below.

Specifically, a solution of Formula 3 (0.100 g, 0.137 mmol) was added to a solution containing the novel ligand (0.044 g, 0.206 mmol) prepared in Preparation Example 1-3 in _{CH 2} Cl _{2 (2.50 mL), and} Stirred for 30 minutes. After stirring, the color of the mixture changed from green to light brown, and the solvent was removed under reduced pressure to give a light brown solid. The light brown solid was dissolved in 0.50 ml benzene, and 20 ml of pentane was added to obtain a yellow solid, which was filtered and washed with pentane (yield=0.079 g, 84%).

[Scheme 7]

Preparation Example 2-4: Preparation of ruthenium-based catalyst 2-4

A ruthenium-based catalyst 2-4 was prepared as shown in Scheme 8 below.

Specifically, a solution of Formula 3 (0.100 g, 0.130 mmol) was added to a solution containing the novel ligand (0.044 g, 0.200 mmol) prepared in Preparation Example 1-4 in _{CH 2} Cl _{2 (2.50 mL), and} Stirred for 30 minutes. After stirring, the color of the mixture changed from green to light brown, and the solvent was removed under reduced pressure to give a light brown solid. The light brown solid was dissolved in 0.50 ml benzene, and 20 ml of pentane was added to obtain a yellow solid, which was filtered and washed with pentane (yield=0.075 g, 79%).

[Scheme 8]

Comparative Example 1: Stability comparison

The reaction rates of the catalysts 2-1 to 2-4 prepared in Preparation Example 2 and the conventional catalyst were compared.

Specifically, the catalyst was added to DCPD, and the temperature change during the ROMP reaction (Scheme 9) was measured and shown in FIGS. 1 and 2 .

[Scheme 9]

As shown in FIG. 2 , the catalysts prepared in Preparation Examples 2-1 and 2-2 exhibited latent behavior while reacting at 60° C. without ROMP reaction of DCPD at 30° C. (room temperature). When 60°C was reached, the ROMP reaction increased to the maximum temperatures of 142°C and 166°C. This may be due to the presence of a donor ligand bound to the ruthenium metal center via a coordination bond. It may not dissociate to generate an active intermediate species to initiate ROMP. The catalysts prepared in Preparation Examples 2-3 and 2-4 were subjected to a ROMP reaction at 30° C. (room temperature), but showed a slow initiation rate for 20 to 25 minutes and the ROMP reaction was performed. In addition, the catalyst prepared in Preparation Example 2-3 reacted after 20 minutes, and the catalyst prepared in Preparation Example 2-4 reacted after 6 minutes. In contrast, the conventional catalysts (Ref 1, existing catalysts 1 to 2) completed the ROMP reaction within 2 minutes. Therefore, in Preparation Examples 2-1 to 2-4 of the present invention, the novel ligand coordinated to the ruthenium center increases the potential behavior of the catalyst without affecting the ROMP activity of the catalyst, including the novel ligand. It was confirmed that the ROMP initiation temperature was increased.

Comparative Example 2: TGA (Thermogravimetric analysis) analysis

The characteristics of the PDCPD and the conversion rate of monomers produced using the catalysts prepared in Preparation Examples 2-1 to 2-3 and the existing catalysts were analyzed using TGA.

Specifically, the TGA analysis is shown in FIG. 3 by analyzing in a nitrogen atmosphere in a temperature range of 30°C to 500°C.

As shown in FIG. 3 , as a result of TGA analysis of the PDCPD prepared using the catalyst prepared in Preparation Examples 2-1 to 2-3 and the conventional catalyst (Ref 1), prepared in Preparation Example 2-1 The PDCPD prepared with the catalyst shows two steps of weight reduction. The first is a weight loss of 25% at 95 to 230°C, which corresponds to the decomposition of small polymer chains and evaporation of unreacted DCPD monomers, and the second stage shows a rapid weight loss after 450°C, which indicates that the polymer bone diameter is higher than 450°C. indicates that it is decomposed into PDCPDs prepared with other catalysts show similar weight loss trends, and weight loss is only observed after 450°C. These results indicate that the catalyst does not affect the PDCPD polymerization process.

Comparative Example 3: DSC (differential scanning calorimetry) analysis

The glass transition temperature (Tg) of the catalyst prepared in Preparation Examples 2-1 to 2-4 and the PDCPD prepared using the conventional catalyst was analyzed by DSC.

Specifically, the glass transition temperature value is the glass temperature found for the PDCPD polymer obtained at 80° C. using the catalyst prepared in Preparation Examples 2-1 to 2-4 and the existing catalyst (Ref) is 144 to 153. ℃ was.

When prepared with the catalysts prepared in Preparation Examples 2-1 to 2-2, the glass transition temperature of PDCPD is lower than when prepared using the catalysts prepared in Preparation Examples 2-3 to 2-4. has a temperature value. This result means that when the ROMP reaction is carried out at a low temperature, the resulting polymer has a lower glass transition temperature value than that of the polymer obtained at a high temperature.

Comparative Example 4: COD (Cyclooctadiene) polymerization

The change during ROMP reaction of COD with the catalysts prepared in Preparation Examples 2-1 to 2-4 and the existing catalyst was investigated.

Specifically, ^{by monitoring by 1} H NMR spectroscopy (C ₆ D ₆ , 27° C.), COD and a catalyst were added 500:1 to perform a ROMP reaction (reaction Scheme 10), and the conversion shown in FIG. 4 is shown.

[Scheme 10]

As shown in FIG. 4, the conventional catalyst (Ref) completely converted COD into the desired product within a short time. The catalysts prepared in Preparation Examples 2-3 and 2-4 were completely converted to monomers after 20 minutes and 15 minutes. In the catalysts prepared in Preparation Examples 2-1 and 2-2, only 48% and 54% of COD were converted after 10 minutes, and completely converted after 45 minutes. In the COD ROMP reaction, it was confirmed that the catalyst of the present invention exhibited a slower initiation rate than the conventional catalyst.

Combining the results of Preparation Examples 1 to 2 and Comparative Examples 1 to 4 of the present invention, the ruthenium-based catalyst having a novel ligand of the present invention has excellent potential in the ROMP reaction, and is stable at room temperature and high temperature, and RIM process It was confirmed that it provides the effect of performing an appropriate pre-treatment process.

From the above description, those skilled in the art to which the present invention pertains will understand that the present invention may be embodied in other specific forms without changing the technical spirit or essential characteristics thereof. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention, rather than the above detailed description, all changes or modifications derived from the meaning and scope of the claims described below and their equivalents.

Claims (7)

A ring-opening polymerization catalyst of dicyclopentadiene (DCPD) or cyclooctadiene (COD) represented by the following Chemical Formulas 1 to 2:
[Formula 1]

[Formula 2]

In the following formula (1),
wherein X is

, or

ego,
wherein Y is

, or

am.
delete delete delete A method for preparing a catalyst for ring-opening polymerization of dicyclopentadiene (DCPD) or cyclooctadiene (COD) according to any one of the following Reaction Schemes 5 to 8.
[Scheme 5]

[Scheme 6]

[Scheme 7]

[Scheme 8]

In Schemes 5 to 8, Py is pyridine. delete delete

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