KR102394369B1 - Preparation method of dimethyl terephthalate - Google Patents

Abstract

The present invention relates to an efficient method for producing dimethyl terephthalate, and according to the present invention, dimethyl terephthalate in high yield can be efficiently produced by using ethylene gas as an oxidizing agent during the aromatization reaction of alicyclic dicarboxylate. there is.

Description

Method for producing dimethyl terephthalate {PREPARATION METHOD OF DIMETHYL TEREPHTHALATE}

The present invention relates to a method for efficiently manufacturing dimethyl terephthalate, which is used as a main component of plastics, coatings, adhesives and paints.

Recently, a technology to replace petroleum-derived substances using biological-derived substances is being studied. Diesel is being developed. In addition, bio-derived materials are being studied to replace not only the energy materials but also the traditional polymer industry. Methylene terephthalate (PTT) is a representative example that has reached the commercialization stage.

Dimethyl terephthalate (DMT) is a representative raw material of polyester, and is a compound having a structure of the following chemical formula (C ₁₀ H ₁₀ O ₄ , molecular weight 194).

Dimethyl terephthalate is used as a main component of plastics, coatings, adhesives and paints, and is also used in various fields such as reducing it to synthesize various types of diols. For example, dimethyl terephthalate is used as a main raw material for synthesizing polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT).

As a method for producing dimethyl terephthalate, it is known that dimethylcyclohex-2-ene-1,4-dicarboxylate is subjected to an aromatization reaction using oxygen as an oxidizing agent. However, such a dimethyl terephthalate manufacturing method has the following problems.

First, during a reaction using oxygen as an oxidizing agent, H ₂ O is inevitably generated, and the generated H ₂ O hydrolyzes dimethyl terephthalate to generate unwanted by-products.

Second, the reduction reaction as well as the oxidation reaction of the precursor proceeds due to hydrogen generated during the oxidation reaction, and the yield is reduced due to many by-products.

International Patent Publication No. WO 2012/082725

The present inventors have discovered that, while studying an efficient method for preparing dimethyl terephthalate, by-products due to the reduction reaction can be minimized by using an unsaturated hydrocarbon as an oxidizing agent during the aromatization reaction.

Accordingly, an object of the present invention is to provide a method for efficiently and economically producing dimethyl terephthalate in high yield.

In order to achieve the above object, the present invention comprises the steps of (1) preparing at least one alicyclic dicarboxylate of a compound of the following formula (1) and a compound of the following formula (2); and (2) performing an aromatization reaction of the alicyclic dicarboxylate under a metal catalyst using an unsaturated hydrocarbon as an oxidizing agent.

According to the method for producing dimethyl terephthalate of the present invention, dimethyl terephthalate can be obtained in high yield by maximally suppressing by-products due to the reduction reaction compared to the conventional method.

Specifically, according to the method of the present invention, by using an unsaturated hydrocarbon as an oxidizing agent (or reducing inhibitor) during the aromatization reaction, hydrogen can be effectively removed in the reaction process to suppress side reactions as much as possible while increasing the yield of the target product, dimethyl terephthalate. there is.

In addition, when an unsaturated hydrocarbon is used as an oxidizing agent, when oxygen is conventionally used as an oxidizing agent, H ₂ O is generated and a problem of causing a side reaction can be solved.

In addition, according to the present invention, although both compounds of Formulas 1 and 2 can be used as starting materials, side reactions can be further suppressed when an aromatization reaction is performed by converting to the compound of Formula 2 above.

The present invention comprises the steps of (1) preparing at least one alicyclic dicarboxylate of a compound of Formula 1 and a compound of Formula 2 below; and (2) performing an aromatization reaction of the alicyclic dicarboxylate under a metal catalyst using an unsaturated hydrocarbon as an oxidizing agent.

Hereinafter, each step will be described in detail.

In step (1), at least one dicarboxylate of the compound of Formula 1 and the compound of Formula 2 is prepared.

That is, as the alicyclic dicarboxylate, the compound of Formula 1 (dimethylcyclohex-2-ene-1,4-dicarboxylate) is prepared, or the compound of Formula 2 (dimethylcyclohex-1-ene-1) ,4-dicarboxylate), or a mixture thereof may be prepared.

As an example, the compound of Formula 2 may be prepared in step (1), and an aromatization reaction of the compound of Formula 2 may be performed in the subsequent step (2).

As another example, preparing the compound of Formula 1 in step (1), and converting the compound of Formula 1 into the compound of Formula 2 between steps (1) and (2) and, in the subsequent step (2), an aromatization reaction of the compound of Formula 2 may be performed.

Since the double bond of the compound of Formula 2 is highly unlikely to undergo a reduction reaction in which hydrogen is added, prepare the compound of Formula 2, or prepare the compound of Formula 1, and then convert the compound of Formula 2 to the ring By further stabilizing the double bond within, unwanted by-products resulting from the hydrogenation reduction reaction can be suppressed.

The conversion of the compound of Formula 1 to the compound of Formula 2 may be performed under a basic catalyst. Examples of the basic catalyst include amines such as triethylamine and diethylamine; alkali alkoxides such as sodium methoxide (NaOMe) and potassium methoxide (KOMe); cycloamines such as 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU); alkali alkanes such as butyl lithium; and mixtures thereof.

In addition, the conversion step may be performed at a temperature of 50 °C or higher, more specifically, at a temperature of 50 to 400 °C, 50 to 300 °C, or 50 to 150 °C. Preferably, the conversion step may be carried out at a temperature of 50 ~ 150 ℃ under a basic catalyst.

In addition, the conversion step may be performed for 1 to 48 hours, more specifically, 2 to 36 hours, 3 to 24 hours, 10 to 24 hours, or 14 to 24 hours, but is not particularly limited.

The conversion step may be carried out only with the reactants without a solvent or may be carried out in a solvent.

Examples of the solvent usable in the conversion step include aromatic solvents such as benzene, toluene, chlorobenzene, cresol, methyl phenyl ester, and xylene; alkyl ether solvents such as tetrahydrofuran, dimethyl ethylene glycol, ethylene glycol dimethyl ether, and diglyme; alkyl acetate solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; N-methylpyrrolidone (NMP); methylformamide; dimethyl sulfoxide; acetonitrile; Hydrocarbons, such as dodecane and hexadecane; and mixtures thereof.

In the step (2), the aromatization reaction of the alicyclic dicarboxylate is performed under a metal catalyst using an unsaturated hydrocarbon as an oxidizing agent.

The "aromatization reaction" refers to a reaction in which a compound having an alicyclic ring is changed into a compound having an aromatic ring composed of the same number of carbon atoms. In the aromatization reaction, dimethyl terephthalate may be obtained by removing four hydrogens from the alicyclic ring of the compound of Formula 1 or 2.

The unsaturated hydrocarbon used in the aromatization reaction may be, for example, an aliphatic unsaturated hydrocarbon, and more specifically, may be at least one selected from the group consisting of ethylene, propylene, isobutene and butadiene. In addition, the unsaturated hydrocarbon may be a gaseous compound.

The metal catalyst used in the aromatization reaction is selected from the group consisting of palladium (Pd), platinum (Pt), nickel (Ni), cobalt (Co), copper (Cu), ruthenium (Ru), complexes thereof, and combinations thereof. It can be any one. Preferably, the metal catalyst may be a palladium-based or platinum-based catalyst.

In addition, the aromatization reaction may be carried out at a temperature of 50 °C or higher, more specifically, at a temperature of 50 to 400 °C, 50 to 300 °C, or 150 to 250 °C.

The aromatization reaction may be performed for 1 to 48 hours, more specifically 2 to 36 hours, 3 to 24 hours, or 10 to 24 hours, but is not particularly limited.

The aromatization reaction may be carried out only with the reactants without a solvent or may be carried out in a solvent.

Examples of the solvent usable for the aromatization reaction include aromatic solvents such as benzene, toluene, chlorobenzene, cresol, methyl phenyl ester, and xylene; alkyl ether solvents such as tetrahydrofuran, dimethyl ethylene glycol, ethylene glycol dimethyl ether, and diglyme; alkyl acetate solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; N-methylpyrrolidone (NMP); methylformamide; dimethyl sulfoxide; acetonitrile; Hydrocarbons, such as dodecane and hexadecane; and mixtures thereof.

Such an aromatization reaction produces very little by-product, for example, dimethylcyclohexane-1,4-dicarboxylate of the following formula 3 as a by-product relative to the weight of the total reaction product is produced within 20%, or within 10% can do.

According to the method for producing dimethyl terephthalate of the present invention, dimethyl terephthalate can be obtained in high yield by maximally suppressing by-products due to the reduction reaction compared to the conventional method.

Specifically, according to the method of the present invention, by using an unsaturated hydrocarbon as an oxidizing agent (or reducing inhibitor) during the aromatization reaction, hydrogen can be effectively removed in the reaction process to suppress side reactions as much as possible while increasing the yield of the target product, dimethyl terephthalate. there is.

In addition, when an unsaturated hydrocarbon is used as an oxidizing agent, when oxygen is conventionally used as an oxidizing agent, H ₂ O is generated and a problem of causing a side reaction can be solved.

In addition, according to the present invention, although both the compounds of Formulas 1 and 2 can be used as starting materials, when the aromatication reaction is performed by converting the compound of Formula 2 to the above, it is preferable because side reactions can be further suppressed.

On the other hand, the compound of Formula 1 (dimethylcyclohex-2-ene-1,4-dicarboxylate) can be obtained commercially or prepared through addition cyclization from dimethyl muconate. The dimethyl muconate is preferably trans, trans-dimethyl muconate may be.

The dimethyl muconate can be prepared from muconic acid by adding a catalyst in a solvent.

As a solvent that can be used for the preparation of such dimethyl muconate, alcohols such as methanol and ethanol; Polar solvents, such as methyl iodide (MeI), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO); alkyl ethers such as tetrahydrofuran (THF), diethyl ether, and dimethyl ethylene glycol; alkyl acetates such as ethyl acetate and methyl acetate; ketones such as methyl ethyl ketone (MEK) and acetone; aromatic solvents such as benzene, toluene, xylene, chlorobenzene, cresol, and methyl phenyl ester; organic solvents such as methylene chloride and chloroform; and a mixed solvent thereof. Preferably, methanol may be used as a solvent for the preparation of dimethyl muconate.

In addition, as a catalyst usable for the preparation of dimethyl muconate, acids such as methanesulfonic acid, p-paratoluenesulfonic acid, phosphoric acid, hydrochloric acid, sulfuric acid; bases such as potassium carbonate and sodium hydroxide; and mixtures thereof. Preferably, sulfuric acid may be used as a catalyst for the production of dimethyl muconate.

According to a preferred embodiment, after adding concentrated sulfuric acid as a catalyst to trans, trans-muconic acid, it is reacted under reflux conditions to prepare trans, trans-dimethyl muconate.

Next, trans, trans- dimethylcyclohex-2-ene-1,4-dicarboxylate can be synthesized from dimethyl muconate through an addition cyclization reaction.

The "addition cyclization reaction" refers to a reaction in which two or more compounds of the same or heterogeneous type are directly combined to form a different type of molecule.

The addition cyclization reaction may be carried out in a solvent, and the solvents that can be used in this case include aromatic solvents such as benzene, toluene, chlorobenzene, cresol, methyl phenyl ester, and xylene; alkyl ether solvents such as tetrahydrofuran, dimethyl ethylene glycol, ethylene glycol dimethyl ether, and diglyme; alkyl acetate solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; N-methylpyrrolidone (NMP); methylformamide; dimethyl sulfoxide; and mixtures thereof.

Preferably, ethylene glycol dimethyl ether may be used as a solvent for the addition cyclization reaction.

In addition, in the addition cyclization reaction, the solvent may be used in an amount of 1 to 200 equivalents, or 10 to 100 equivalents, based on dimethyl muconate.

The concentration of dimethyl muconate diluted in the solvent for the addition cyclization reaction may be 0.1 to 3.5 M, more specifically 0.1 to 3.0 M, 0.2 to 2.5 M, 0.2 to 2.0 M or 0.2 to 1.5 M. Preferably, dimethyl muconate may be diluted in a solvent to a concentration of 1.0 M for the addition cyclization reaction.

In addition, the addition cyclization reaction may be performed in the presence of ethylene gas. In this case, the ethylene gas may be added at a pressure of 1 bar or more, more specifically 1 to 20 bar, 10 to 19 bar, or 15 to 18 bar. Preferably, the ethylene gas may be added at a pressure of 17 bar.

In addition, the addition cyclization reaction may be carried out at a temperature of 100 °C or higher, more specifically 100 to 400 °C, 130 to 300 °C, or 150 to 250 °C. In addition, the addition cyclization reaction may be performed for 1 to 48 hours, more specifically, for 2 to 36 hours, 3 to 24 hours, 4 to 12 hours, or 5 to 10 hours. Preferably, the addition cyclization reaction may be performed at 200° C. for 8 hours.

According to a preferred embodiment, trans,trans-dimethyl muconate is dissolved in ethylene glycol dimethyl ether to prepare a trans,trans-dimethyl muconate solution of about 1.0 M, and then ethylene gas is added to the solution at a pressure of about 17 bar. After addition, dimethylcyclohex-2-ene-1,4-dicarboxylate may be obtained by performing an addition cyclization reaction at about 200° C. for about 8 hours in a high-pressure reactor.

Hereinafter, the present invention will be described by way of more specific examples.

However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

Preparation Example 1: Trans, trans - Preparation of dimethyl muconate

100 g of trans, trans-muconic acid was dissolved in 1,000 mL of methanol, and 3 g of concentrated sulfuric acid was added as a catalyst and reacted under reflux conditions to obtain 116 g of trans, trans-dimethyl muconate.

Preparation Example 2: Preparation of dimethylcyclohex-2-ene-1,4-dicarboxylate

110 g of trans, trans-dimethyl muconate obtained in Preparation Example 1 was dissolved in 1,300 mL of ethylene glycol dimethyl ether to prepare a 0.5 M trans, trans-dimethyl muconate solution. Thereafter, ethylene gas was injected into the solution, and an addition cyclization reaction was performed at 200° C. for 8 hours while pressurized at a pressure of 17 bar in a high-pressure reactor (Parr reactor, 4533HP). As a result, 125 g of dimethylcyclohex-2-ene-1,4-dicarboxylate was obtained.

Preparation Example 3: Preparation of dimethylcyclohex-1-ene-1,4-dicarboxylate

Put 160 g of dimethylcyclohex-2-ene-1,4-dicarboxylate obtained in Preparation Example 2 in a 250 mL round-bottom flask, and 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU) 0.13 g was added. The reaction was carried out without a solvent at 130° C. for 4 hours and then cooled to room temperature. After confirming 100% conversion using GC-MS, it was used in the subsequent reaction without a separate purification process.

Example 1: Preparation of dimethyl terephthalate

Into a 250 mL round-bottom flask, 100 g of dimethylcyclohex-2-ene-1,4-dicarboxylate obtained in Preparation Example 2 was added, and 2.5 g of Pd/C (10% Pd) as a catalyst without a solvent was added. The reaction mixture was gradually heated to 250° C. while bubbling ethylene gas, followed by reaction for 3 hours. As a result of confirmation by GC-MS, the starting material, dimethylcyclohex-2-ene-1,4-dicarboxylate, completely disappeared, and the target compound, dimethyl terephthalate, and the by-product, dimethylcyclohexane-1,4-dicarboxylate, were was obtained.

Example 2: Preparation of dimethyl terephthalate

Into a 250 mL round-bottom flask, 100 g of dimethylcyclohex-1-ene-1,4-dicarboxylate obtained in Preparation Example 3 was added, and 2.5 g of Pd/C (10% Pd) as a catalyst without a solvent was added. The reaction mixture was gradually heated to 250° C. while bubbling ethylene gas, followed by reaction for 16 hours. As a result of confirmation by GC-MS, the starting material, dimethylcyclohex-1-ene-1,4-dicarboxylate, completely disappeared, and the target compound, dimethyl terephthalate, and the by-product, dimethylcyclohexane-1,4-dicarboxylate, disappeared. was obtained.

Example 3: Preparation of dimethyl terephthalate

Put 10 g of dimethylcyclohex-1-ene-1,4-dicarboxylate obtained in Preparation Example 3 in a 250 mL round-bottom flask, 100 mL of hexadecane as a solvent and Pd/C (10% Pd) 0.25 as a catalyst g was added. The reaction mixture was gradually heated to 250° C. while bubbling ethylene gas, followed by reaction for 20 hours. As a result of confirmation by GC-MS, the starting material, dimethylcyclohex-1-ene-1,4-dicarboxylate, completely disappeared, and the target compound, dimethyl terephthalate, and the by-product, dimethylcyclohexane-1,4-dicarboxylate, disappeared. was obtained.

Example 4: Preparation of dimethyl terephthalate

Put 20 g of dimethylcyclohex-1-ene-1,4-dicarboxylate obtained in Preparation Example 3 in a 250 mL round-bottom flask, 100 mL of hexadecane as a solvent and Pd/C (10% Pd) 0.5 as a catalyst g was added. The reaction mixture was gradually heated to 250° C. while bubbling ethylene gas, followed by reaction for 22 hours. As a result of confirmation by GC-MS, the starting material, dimethylcyclohex-1-ene-1,4-dicarboxylate, completely disappeared, and the target compound, dimethyl terephthalate, and the by-product, dimethylcyclohexane-1,4-dicarboxylate, disappeared. was obtained.

Example 5: Preparation of dimethyl terephthalate

Put 30 g of dimethylcyclohex-1-ene-1,4-dicarboxylate obtained in Preparation Example 3 in a 250 mL round-bottom flask, 100 mL of hexadecane as a solvent and Pd/C (10% Pd) 0.75 as a catalyst g was added. The reaction mixture was gradually heated to 250° C. while bubbling ethylene gas, and then reacted for 24 hours. As a result of confirmation by GC-MS, the starting material, dimethylcyclohex-1-ene-1,4-dicarboxylate, completely disappeared, and the target compound, dimethyl terephthalate, and the by-product, dimethylcyclohexane-1,4-dicarboxylate, disappeared. was obtained.

Example 6: Preparation of dimethyl terephthalate

Put 30 g of dimethylcyclohex-2-ene-1,4-dicarboxylate obtained in Preparation Example 2 in a 250 mL round-bottom flask, 100 mL of hexadecane as a solvent and Pd/C (10% Pd) 0.75 as a catalyst g was added. The reaction mixture was gradually heated to 250° C. while bubbling ethylene gas, followed by reaction for 6 hours. As a result of confirmation by GC-MS, the starting material, dimethylcyclohex-2-ene-1,4-dicarboxylate, completely disappeared, and the target compound, dimethyl terephthalate, and the by-product, dimethylcyclohexane-1,4-dicarboxylate, were was obtained.

Comparative Example 1 : Preparation of dimethyl terephthalate

Into a 250 mL round-bottom flask, 100 g of dimethylcyclohex-2-ene-1,4-dicarboxylate obtained in Preparation Example 2 was added, and 2.5 g of Pd/C (10% Pd) as a catalyst without a solvent was added. The reaction mixture was gradually heated to 250° C. while bubbling ethylene gas, followed by reaction for 4 hours. As a result of confirmation by GC-MS, the starting material, dimethylcyclohex-2-ene-1,4-dicarboxylate, completely disappeared, and the target compound, dimethyl terephthalate, and the by-product, dimethylcyclohexane-1,4-dicarboxylate, were was obtained.

Comparative Example 2 : Preparation of dimethyl terephthalate

Into a 250 mL round-bottom flask, 100 g of the dimethylcyclohex-1-ene-1,4-dicarboxylate obtained in Preparation Example 3 was added, and 2.5 g of Pd/C (10% Pd) as a catalyst without a solvent was added. The reaction mixture was gradually heated to 250° C. and reacted for 4 hours. As a result of confirmation by GC-MS, the starting material, dimethylcyclohex-1-ene-1,4-dicarboxylate, completely disappeared, and the target compound, dimethyl terephthalate, and the by-product, dimethylcyclohexane-1,4-dicarboxylate, disappeared. was obtained.

Comparative Example 3 : Preparation of dimethyl terephthalate

Put 30 g of dimethylcyclohex-1-ene-1,4-dicarboxylate obtained in Preparation Example 3 in a 250 mL round-bottom flask, 100 mL of hexadecane as a solvent and Pd/C (10% Pd) 0.75 as a catalyst g was added. The reaction mixture was gradually heated to 250° C. and reacted for 4 hours. As a result of confirmation by GC-MS, the starting material, dimethylcyclohex-1-ene-1,4-dicarboxylate, completely disappeared, and the target compound, dimethyl terephthalate, and the by-product, dimethylcyclohexane-1,4-dicarboxylate, disappeared. was obtained.

GC-MS analysis

Gas chromatography-mass spectrometry (GC-MS) was performed under the following conditions to analyze the ratio of the target compound obtained in Examples and Comparative Examples, dimethyl terephthalate, and the by-product, dimethylcyclohexane-1,4-dicarboxylate. carried out.

- Instrument: Claus 680 GC and SQ 8 MS from Perkin Elmer

- Column: DB-5 (15 m × 0.25 mm × 0.10 μm, Agilent Technologies, USA)

Specifically, when the sum of the GC-MS area values of dimethyl terephthalate and dimethylcyclohexane-1,4-dicarboxylate was 100%, the ratio of each area value was calculated.

The aromatization reaction conditions of Examples and Comparative Examples, and the results of GC-MS are shown in Table 1 below.

division
aromatization
reactant
menstruum
reactant concentration
(M)
unsaturated
carbonization
Hydrogen
reaction
time
(h) dimethyl
terephthal
rate
(%) dimethylcyclo
Hexane-1,4-
dicarboxyl
Rate (%) Example
One Dimethylcyclohex-2-ene
-1,4-dicarboxylate - - ethylene 3 58 42 Example
2 Dimethylcyclohex-1-ene
-1,4-dicarboxylate - - ethylene 16 83 17 Example
3 Dimethylcyclohex-1-ene
-1,4-dicarboxylate hex
Deccan 0.5 ethylene 20 94 6 Example
4 Dimethylcyclohex-1-ene
-1,4-dicarboxylate hex
Deccan 1.0 ethylene 22 94 6 Example
5 Dimethylcyclohex-1-ene
-1,4-dicarboxylate hex
Deccan 1.5 ethylene 24 93 7 Example
6 Dimethylcyclohex-2-ene
-1,4-dicarboxylate hex
Deccan 1.5 ethylene 6 75 25 comparative example
One Dimethylcyclohex-2-ene
-1,4-dicarboxylate - - - 4 40 60 comparative example
2 Dimethylcyclohex-1-ene
-1,4-dicarboxylate - - - 4 42 58 comparative example
3 Dimethylcyclohex-1-ene
-1,4-dicarboxylate hex
Deccan - - 4 45 55

As shown in Table 1, when ethylene gas was used as an oxidizing agent during the aromatization reaction as in Examples 1 to 6, the production of dimethylcyclohexane-1,4-dicarboxylate due to a side reaction was suppressed, so that dimethyl terephthalate yield was high.

In addition, in the case of an example in which an aromatization reaction was performed after conversion to dimethylcyclohex-1-ene-1,4-dicarboxylate or the reaction was performed in a solvent, the side reaction was further suppressed, and the yield of dimethyl terephthalate was higher. .

On the other hand, when the aromatization reaction was performed without using ethylene gas as an oxidizing agent as in Comparative Examples 1 to 3, the production of dimethylcyclohexane-1,4-dicarboxylate due to a side reaction increased and the yield of dimethyl terephthalate was increased. It was low.

Claims (9)

(1) preparing at least one alicyclic dicarboxylate of a compound of Formula 1 and a compound of Formula 2; and
(2) performing an aromatization reaction of the alicyclic dicarboxylate under a metal catalyst using an unsaturated hydrocarbon as an oxidizing agent,
The unsaturated hydrocarbon is at least one selected from the group consisting of ethylene, propylene, isobutene and butadiene, a method for producing dimethyl terephthalate:

.
delete The method of claim 1,
The method for producing dimethyl terephthalate, wherein the metal catalyst is a palladium-based or platinum-based catalyst.
The method of claim 1,
The method for producing dimethyl terephthalate, wherein the aromatization reaction is carried out at a temperature of 50 ~ 300 ℃.
The method of claim 1,
Preparing the compound of Formula 2 in step (1),
A method for producing dimethyl terephthalate, performing an aromatization reaction of the compound of Formula 2 in the step (2).
The method of claim 1,
Preparing the compound of Formula 1 in step (1),
Between the steps (1) and (2), it further comprises converting the compound of Formula 1 to the compound of Formula 2,
A method for producing dimethyl terephthalate, performing an aromatization reaction of the compound of Formula 2 in the step (2).
7. The method of claim 6,
The method for producing dimethyl terephthalate, wherein the conversion step is carried out at a temperature of 50 ~ 150 ℃ under a basic catalyst.
7. The method of claim 6,
A method for producing dimethyl terephthalate, wherein the compound of Formula 1 is prepared through an addition cyclization reaction from dimethyl muconate.
9. The method of claim 8,
The dimethyl mu-conate is trans, trans-dimethyl mu-conate, the method for producing dimethyl terephthalate.