KR20230158775A - Catalyst for ortho-alkylarion reaction and preparation method of ortho-alkylarion reaction product using the same - Google Patents

Abstract

The present invention relates to a catalyst composition for producing an ortho-alkylation reaction product and a method for producing an ortho-alkylation reaction product using the same. More specifically, in the selective ortho-alkylation reaction of a phenolic compound, the ortho-alkylation reaction product can achieve high selectivity and conversion rate. It relates to a catalyst composition for preparing an alkylation reaction product and a method for producing an ortho-alkylation reaction product using the same.

Description

Ortho-alkylation reaction catalyst and method for producing ortho-alkylation reaction products using the same {CATALYST FOR ORTHO-ALKYLARION REACTION AND PREPARATION METHOD OF ORTHO-ALKYLARION REACTION PRODUCT USING THE SAME}

The present invention relates to an ortho-alkylation reaction catalyst and a method for producing an ortho-alkylation reaction product using the same. More specifically, in the ortho-alkylation reaction of a phenolic compound, an ortho-alkylation reaction product can be obtained with high selectivity and conversion rate. It relates to an ortho-alkylation reaction catalyst and a method for producing an ortho-alkylation reaction product using the same.

Alkylated hydroxyaromatic compounds have a variety of uses, and they are typically prepared by the gas phase reaction of phenol and methanol. In addition, through additional alkylation reactions, compounds with various structures can be produced, and they are easy to apply to high-performance thermoplastic product groups.

These additional alkylation reactions are typically performed in the presence of magnesium-based compounds, and various studies have been conducted to optimize the performance of magnesium-based catalysts.

In an alkylation reaction, a magnesium-based catalyst is required to have high activity, a long active life, and high selectivity for the desired reaction product. Most of the alkylation catalysts used in the past produced large quantities of para-alkylated products, but various studies have been conducted to obtain more useful ortho-alkylated products in high yield.

However, the prior art is a technique of using a combination of cocatalyst compounds in addition to the magnesium-based catalyst, changing the composition of the catalyst, or changing the reaction conditions, and the ortho-alkylation product is produced with the desired precision and high selectivity and yield. There was a problem that made it difficult to obtain.

Accordingly, in the ortho-alkylation reaction, there is a need to develop improved catalysts in terms of catalyst selectivity, catalyst activity, production yield, cost reduction, and total productivity.

The present invention provides an ortho-alkylation reaction catalyst capable of achieving excellent conversion and yield in the production of selective ortho-alkylation reaction products.

Additionally, the present invention provides a method for producing an ortho-alkylation reaction product using the catalyst.

In order to solve the above problem, the present invention,

Comprising magnesium oxide having a bimodal pore structure and a BET specific surface area of 100 m ² /g to 180 m ² /g,

An ortho-alkylation reaction catalyst is provided.

In addition, the present invention,

Comprising a monomer composition comprising the above-described ortho-alkylation reaction catalyst and a meta-alkyl substituted phenolic monomer,

An ortho-alkylation reaction composition is provided.

In addition, the present invention,

Comprising an alkylation reaction of a monomer composition comprising a meta-alkyl substituted phenolic monomer in the presence of the ortho-alkylation reaction catalyst described above,

A method for preparing an ortho-alkylation reaction product is provided.

The ortho-alkylation reaction catalyst according to the present invention exhibits high catalytic activity by using magnesium oxide having specific physical properties and pore structure, and when using it to prepare an ortho-alkylation reaction product, it exhibits significantly high selectivity and conversion rate. .

The ortho-alkylation reaction catalyst according to the present invention exhibits high catalytic activity alone without the use of a separate cocatalyst or additional additive, and when using it to prepare an ortho-alkylation reaction product, it exhibits significantly higher selectivity and conversion rate. indicates.

Figure 1 is a graph showing the selectivity of reaction products prepared using ortho-alkylation reaction catalysts of Examples and Comparative Examples of the present invention.
Figure 2 is an XDR graph of the ortho-alkylation reaction catalyst of Examples and Comparative Examples of the present invention.
Figure 3 is a graph showing pore distribution according to N ₂ adsorption-desorption analysis of ortho-alkylation reaction catalysts of Examples and Comparative Examples of the present invention.

Since the present invention can be subject to various changes and can take various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

Additionally, the terminology used herein is only used to describe exemplary embodiments and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as “comprise,” “comprise,” or “have” are intended to designate the presence of implemented features, steps, components, or a combination thereof, and are intended to indicate the presence of one or more other features or steps, It should be understood that the existence or addition possibility of components or combinations thereof is not excluded in advance.

Additionally, in the present invention, when each component is referred to as being formed “on” or “on” each component, it means that each component is formed directly on each component, or that another component is formed on each component. This means that it can be additionally formed between layers, on an object, or on a substrate.

Magnesium-based catalysts typically used in alkylation reactions are required to have high activity, long activity life, and high selectivity for the desired reaction product. Most of the alkylation catalysts used in the past produced large quantities of para-alkylated products, but various studies have been conducted to obtain more useful ortho-alkylated products with high selectivity.

However, the prior art is a technique of using a combination of cocatalyst compounds in addition to the magnesium-based catalyst, changing the composition of the catalyst, or changing the reaction conditions, and with this technique, the ortho-alkylation product is produced with the desired precision and high selectivity and conversion rate. There was a problem that made it difficult to obtain.

Additionally, in order to solve this problem, the present inventors confirmed that significantly higher catalytic activity in the alkylation reaction can be achieved by setting the BET specific surface area and pore structure of the magnesium oxide catalyst to a specific range. The ortho-alkylation reaction catalyst according to the present invention exhibits excellent catalytic activity even as a single catalyst without using an additional cocatalyst or adjusting the reaction conditions, and when using it to produce an ortho-alkylation reaction product, a significantly higher The present invention was completed by discovering that selectivity and conversion rate could be achieved.

(Ortho-alkylation reaction catalyst)

The ortho-alkylation reaction catalyst according to one embodiment of the invention has a bimodal pore structure and includes magnesium oxide having a BET specific surface area of 100 m ² /g to 180 m ² /g.

In general, the catalytic activity of a catalyst is determined by reaction conditions or catalyst acid-base characteristics. In the alkylation reaction of meta-alkyl substituted phenolic monomers, if the catalyst has basic characteristics, it perpendicularly adsorbs the reactants to ortho-C- It favors alkylation (see Figure (a) below), and accordingly, the ortho-alkylation reaction catalyst according to the present invention contains a magnesium oxide (MgO) component.

The magnesium oxide has a bi-modal pore structure, specifically a bi-modal form of mesopores, and thus facilitates diffusion of reactants so that the reaction can be carried out effectively. make it possible In addition, by simultaneously satisfying the BET specific surface area within the above-mentioned specific range, it has excellent catalytic activity in the ortho-alkylation reaction and can exhibit high selectivity, conversion, and yield.

Typically, the larger the BET specific surface area, the greater the active point of the catalyst, but in the case of a single-mold type, even if the BET specific surface area increases, diffusion of reactants is not smooth, making it difficult to carry out the reaction to the desired degree.

Preferably, in the bi-modal pore structure, the first pore may have a diameter of 2 nm to 10 nm, and the second pore may have a diameter of 10 nm to 50 nm, and more preferably, the first pore may have a diameter of 2 nm to 10 nm. The diameter of one pore may be 4 nm to 8 nm, and the diameter of the second pore may be 20 nm to 45 nm or 35 nm to 45 nm. A bimodal pore structure with a diameter in the above range can achieve the desired excellent catalytic activity, improved selectivity, conversion rate, and yield.

The magnesium oxide satisfies the BET specific surface area of 100 m ² /g to 180 m ² /g, and has excellent catalytic activity due to its relatively large specific surface area and many reaction active sites. At the same time, as mentioned above, it has a bimodal pore structure and facilitates diffusion of reactants, allowing the reaction to be carried out effectively. Accordingly, it has excellent catalytic activity in the ortho-alkylation reaction and can exhibit improved selectivity, conversion rate, and yield. When the BET specific surface area is less than 100 m ² /g, the number of reaction active sites is significantly reduced and the reactant conversion rate is lowered, making it difficult to achieve the desired activity. In addition, when the BET specific surface area exceeds 180 m ² /g, the reaction active point increases, but first pores are mainly formed and reactant/product diffusion is not smooth, making it difficult to achieve high activity.

Preferably, the BET specific surface area of the magnesium oxide may be 130 m ² /g to 180 m ² /g, more preferably 130 m ² /g to 150 m ² /g, within the above range. This is desirable because it can achieve excellent catalytic activity without any problems.

(Ortho-alkylation reaction composition)

According to one embodiment of the invention, the ortho-alkylation reaction composition includes a monomer composition including the above-described ortho-alkylation reaction catalyst and a meta-alkyl substituted phenolic monomer.

The ortho-alkylation reaction catalyst has a bimodal pore structure and includes magnesium oxide with a BET specific surface area of 100 m ² /g to 180 m ² /g, and all of the above can be equally applied.

Specifically, magnesium oxide has a bi-modal pore structure, and specifically has a bi-modal form of mesopores, thereby facilitating the diffusion of reactants and facilitating the reaction. enable it to be carried out effectively. In addition, by simultaneously satisfying the BET specific surface area within the above-mentioned specific range, it is possible to have excellent catalytic activity in the ortho-alkylation reaction and to exhibit high selectivity and conversion rate.

In the monomer composition, the meta-alkyl substituted phenol-based monomer may be meta-cresol (m-cresol).

The monomer composition further includes alkanol and distilled water (DI Water) in addition to the meta-alkyl substituted phenol monomer, and an alkyl group can be introduced through reaction with the alkanol, and the distilled water is used together, It is preferable because it can suppress the decomposition reaction of alkanol. The alkanol may preferably be methanol.

The monomer composition may preferably contain phenol-based monomer:alkanol:distilled water in an amount of 1:3 to 10:1 to 5 parts by weight, more preferably 1:4 to 6:1 to 3 parts by weight. You can. At this time, if the content of alkanol is included in a small amount outside the above range, the alkylation mediator (agent) is small and the conversion rate is lowered, and if distilled water is included in a small amount outside the above range, the decomposition reaction of alkanol can be suppressed. The effect is reduced, and if alkanol or distilled water is included in excess beyond the above range, it may compete with the phenol-based monomer and adsorb at the catalyst active site, causing a problem of reduced reactivity.

When included in the above content range, it is preferable because an ortho-alkylation reaction product can be prepared with the desired selectivity and conversion rate.

(Method for producing ortho-alkylation reaction product)

According to one embodiment of the invention, a method for producing an ortho-alkylation reaction product includes an alkylation reaction of a monomer composition comprising a meta-alkyl substituted phenolic monomer in the presence of the above-described ortho-alkylation reaction catalyst. Specifically, the method for producing an ortho-alkylation reaction product may be performed using an ortho-alkylation reaction composition containing the above-described ortho-alkylation reaction catalyst. All of the above-mentioned information regarding the catalyst and reaction composition may be equally applied.

The ortho-alkylation reaction catalyst has a bimodal pore structure and includes magnesium oxide with a BET specific surface area of 100 m ² /g to 180 m ² /g, and all of the above can be equally applied.

Specifically, magnesium oxide has a bi-modal pore structure, and specifically has a bi-modal form of mesopores, thereby facilitating the diffusion of reactants and facilitating the reaction. enable it to be carried out effectively. In addition, by simultaneously satisfying the BET specific surface area within the above-mentioned specific range, it is possible to have excellent catalytic activity in the ortho-alkylation reaction and to exhibit high selectivity and conversion rate.

In the method for producing the ortho-alkylation reaction product, the meta-alkyl substituted phenolic monomer of the monomer composition may be meta-cresol (m-cresol).

The method for producing the ortho-alkylation reaction product can exhibit high selectivity and conversion rate of the desired ortho-alkylation reaction product by using a reaction composition containing the above-described catalyst.

The ortho-alkylation reaction products include, for example, 2,5-dimethylphenol, 2,3-dimethylphenol, 2,3,6-trimethylphenol, 3-methylanisole, 3,4-dimethylphenol and tetramethyl It may be one or more types selected from the group consisting of phenol, and may be prepared, for example, by selectively substituting an alkyl group at the ortho position in m-cresol through a multi-step reaction as follows.

The alkylation reaction may be preferably performed at 350°C to 550°C, and more preferably at 350°C to 550°C. At this time, if the temperature is less than 350°C, the alkylation reaction may not be sufficiently activated, and if it exceeds 550°C, many by-products due to overreaction will be generated.

The alkylation reaction may be performed under inert conditions, for example, in the presence of an inert carrier gas. As the inert carrier gas, nitrogen, helium, neon, argon, etc. can be used, preferably nitrogen. By carrying out the above conditions, it is preferable to prepare an ortho-alkylation reaction product with desired selectivity and conversion rate.

The alkylation reaction may preferably be performed using a continuous flow gas phase reactor. In this case, the monomer composition is introduced into the continuous flow gas phase reactor at an LHSV of 0.5 hr ^-1 to 2.0 hr ^-1 . It can be performed by injecting liquid hourly space velocity. At this time, if it is outside the above space velocity range, it may be difficult to obtain the product smoothly because the reactant is not sufficiently activated at the catalyst active site, and the activity or selectivity of the catalyst may be lowered, resulting in a decrease in the amount of product.

By carrying out the above conditions, it is preferable to prepare an ortho-alkylation reaction product with desired selectivity and conversion rate.

Hereinafter, the operation and effects of the invention will be described in more detail through specific examples of the invention. However, these examples are merely presented as examples of the invention, and the scope of the invention is not determined by them.

[Examples and Comparative Examples]

Example 1

The alkylation reaction of m-cresol was performed using a continuous flow gas phase reactor. First, the magnesium oxide component (MgO-1, crystalline structure: MgO) having the physical properties shown in Table 1 was manufactured in granule form (212 - 425 um), and then made into stainless steel with a diameter of 1/2 inch x 50 cm in length. After filling a tube-type reactor with 1g of catalyst, it was installed in the main furnace.

Afterwards, N ₂ , a carrier gas, was flowed using a mass flow controller (MFC) (37.5 cc/min), and for catalyst activation, the inside of the reactor was raised to the activation temperature (450 ℃) and maintained for 1 hour. I ordered it. Afterwards, the monomer composition (12.5 mg/min, m-cresol : Methanol : DIwater = 1:5:1, LHSV 0.75/h) was passed through a pre-heater (250°C), vaporized, and then added. A reaction composition including a catalyst and a monomer composition was introduced into the reactor, and then an alkylation reaction (450° C., maintained at normal pressure) was performed for 5 hours to obtain a reaction product.

The product during the reaction was collected in liquid form (IPA (isopropyl alcohol) was used as a solvent) for analysis.

Example 2 and Comparative Examples 1 to 9

The alkylation reaction was performed in the same manner as in Example 1 except that the magnesium oxide component was changed as shown in Table 1 below, and a reaction product was obtained.

Experimental Example 1: Analysis of physical properties of catalyst

(1) XRD analysis

The crystallite structure of the catalyst used in the examples and comparative examples was confirmed through XRD analysis, and the crystallite size was calculated through the Scherrer equation using the maximum peak value of the XRD patterns, and the results are shown in Table 1 and shown in Figure 2.

At this time, K = 0.89 (the shape factor of the average crystallite), L = 1.5418 (the wavelength for Cu Kα), and FWHM represents the full width half maximum of the peak, θ = maximum peak position.

(2) N ₂ adsorption-desorption analysis

The BET (Brunauer-Emmett-Teller) surface area, pore volume, and size distribution of the catalyst used in the Examples and Comparative Examples were confirmed through N ₂ adsorption-desorption analysis.

The BET surface area was calculated using the adsorption value of P/P0 = 0.05-0.3, and the pore volume and size distribution were calculated using the desorption value, and the results are shown in Table 1 and Figure 3.

division type crystallite size, nm BET surface area,
^m2 /g Total Pore Volume, ^cm3 /g Pore Size,
nm Example 1 Mg0-1 9 144.4 0.72 6, 40 Example 2 Mg0-9 10 134.2 0.7 6, 40 Comparative Example 1 Mg0-2 17 44.3 0.4 50 Comparative Example 2 Mg0-3 37 32.6 0.39 60 Comparative Example 3 Mg0-4 10 125.9 0.46 10 Comparative Example 4 Mg0-5 12 107.7 0.29 7 Comparative Example 5 Mg0-6 40 25.7 0.2 25 Comparative Example 6 Mg0-7 5.4 195.4 0.77 4, 6 Comparative Example 7 Mg0-8 5.4 188.3 0.82 4, 6 Comparative Example 8 Mg0-10 13 102.7 0.72 8, 40 Comparative Example 9 Mg0-11 20 34.1 0.41 60

Experimental Example 2: Analysis of ortho-alkylation reaction products

The liquid containing the reaction products prepared in Examples and Comparative Examples was analyzed using a gas chromatography device (GC) equipped with a FID (Flame Ionization detector) detector, and from the GC results, m-cresol conversion rate and Target product ( The selectivity of 2,3,6-TMP, 2,5-DMP, 2,3-DMP) was calculated using Equation 1 and Equation 2 below, and the results are shown in Table 2.

Target products were defined as 2,3,6-TMP, which is the final target product, and 2,5-DMP and 2,3-DMP, which are intermediate substances and can obtain final products through additional reactions.

[Equation 1]

[Equation 2]

division catalyst m-cresol conversion rate Selectivity (mol%) Target product A B C D E F G Example 1 Mg0-1 88.1 95.3 49.7 12.7 32.9 0.6 0.4 0.2 1.3 Example 2 Mg0-9 79.8 95.6 50.3 13.6 31.7 0.6 0.6 0.1 1.4 Comparative Example 1 Mg0-2 46.1 92.6 62.8 18.7 11.0 1.8 2.3 1.2 - Comparative Example 2 Mg0-3 24.2 97.7 68.7 24.7 4.4 0.2 0.7 1.0 - Comparative Example 3 Mg0-4 43.4 95.0 65.4 20.6 8.9 0.8 2.2 0.5 0.1 Comparative Example 4 Mg0-5 35.5 91.5 63.5 20.5 7.4 0.6 4.5 2.9 0.5 Comparative Example 5 Mg0-6 44.5 96.1 66.8 20.1 9.2 0.7 1.4 0.8 - Comparative Example 6 Mg0-7 32.9 95.2 66.7 22.3 6.1 1.6 2.5 - - Comparative Example 7 Mg0-8 32.5 94.6 66.4 21.8 6.4 1.5 2.7 0.3 0.1 Comparative Example 8 Mg0-10 52.7 94.0 63.9 19.4 10.7 1.3 1.9 0.4 0.4 Comparative Example 9 Mg0-11 31.7 92.3 65.0 20.7 6.6 1.6 3.4 0.8 0.4

As can be seen from the experimental data in Table 2, the catalyst containing magnesium oxide having specific physical properties and pore structure of the present invention exhibits high catalytic activity even with a single catalyst, and when using this to prepare an ortho-alkylation reaction product , it was confirmed that it can exhibit significantly high selectivity and conversion rate.

Claims (13)

Comprising magnesium oxide having a bimodal pore structure and a BET specific surface area of 100 m ² /g to 180 m ² /g,
Ortho-alkylation reaction catalyst.
According to paragraph 1,
In the bi-modal pore structure,
The diameter of the first pore is 2 nm to 10 nm,
The diameter of the second pore is 10 nm to 50 nm,
Ortho-alkylation reaction catalyst.
According to paragraph 1,
The BET specific surface area is 130 m ² /g to 180 m ² /g,
Ortho-alkylation reaction catalyst.
Comprising a monomer composition comprising an ortho-alkylation reaction catalyst according to claim 1 and a meta-alkyl substituted phenolic monomer,
Ortho-alkylation reaction composition.
According to paragraph 4,
The meta-alkyl substituted phenolic monomer is meta-cresol,
Ortho-alkylation reaction composition.
According to paragraph 4,
The monomer composition further includes alkanol and distilled water,
Ortho-alkylation reaction composition.
According to clause 6,
The monomer composition includes phenol-based monomer: alkanol: distilled water in an amount of 1:3 to 10:1 to 5 parts by weight.
Ortho-alkylation reaction composition.
According to clause 6,
The monomer composition includes phenol-based monomer: alkanol: distilled water in a ratio of 1:4 to 6:1 to 3 parts by weight.
Ortho-alkylation reaction composition.
Comprising an alkylation reaction of a monomer composition comprising a meta-alkyl substituted phenolic monomer in the presence of an ortho-alkylation reaction catalyst according to claim 1,
Method for preparing ortho-alkylation reaction product.
According to clause 9,
The alkylation reaction is carried out at 350 to 550 ° C.
Method for preparing ortho-alkylation reaction product.
According to clause 9,
The alkylation reaction is performed using a continuous flow gas phase reaction device,
Method for preparing ortho-alkylation reaction product.
According to clause 11,
The monomer composition is injected into the continuous flow gas phase reaction device at a liquid hourly space velocity (LHSV) of 0.5 hr ^-1 to 2.0 hr ^-1 .
Method for preparing ortho-alkylation reaction product.
According to clause 9,
The ortho-alkylation reaction product is a group consisting of 2,5-dimethylphenol, 2,3-dimethylphenol, 2,3,6-trimethylphenol, 3-methylanisole, 3,4-dimethylphenol and tetramethylphenol One or more types selected from,
Method for preparing ortho-alkylation reaction product.