KR101955417B1 - Method of producing phenol alkoxylate - Google Patents

Abstract

The alkylene oxide addition method of the present invention is characterized in that an alkylene carbonate is used as a reactant for the alkylene oxide addition so that the repeating unit of the oxyalkylene group bonded to the styrenated phenol can be controlled quantitatively and precisely, It is easy to handle reactants and there is no need for a high-pressure reaction device for supplying and controlling reactants. Further, since the basic metal supported catalyst is used in the present invention, it is easy to separate the catalyst in the reaction process and the neutralization process after the reaction according to the use of the catalyst is not necessary.

Description

TECHNICAL FIELD The present invention relates to a method for producing an alkylene oxide addition phenol,

The present invention relates to a process for preparing an alkylene oxide addition phenol.

Additives are used in manufacturing because plastic materials have poor performance in safety, color, strength and other characteristics. Amines, phenols, and phosphorus additives are often used as additives, and they are mainly used as antioxidants. Styrenated phenol, which is typically used in plastics, can be synthesized by alkylation of phenol with styrene.

In the synthesis of styrenated phenols using an alkylation reaction, a mixture comprising phenol having one alkylated functional group, phenol having two alkylated functional groups, and phenol having three alkylated functional groups may be produced. Di-styrenated phenol, which is a phenol having two alkylated functional groups, or a mixture of the di-styrenated phenol having a composition of 60% or more is used as a main ingredient of a nonionic surfactant such as styrenated phenol alkoxylate , Which is due to the ease of controlling the molecular weight of the di-styrenated phenol.

Nonionic surfactants such as styrenated phenol alkoxylates are mainly used in the display industry and are widely used in the production of notebooks, mobile phones, monitors, TVs, and the like, such as active matrix organic light-emitting diodes (AMOLEDs) and flexible- -AMOLED) is used as a color filter for a LCD panel and a developer for a thin film transistor (TFT).

Generally, styrenated phenol alkoxylates are synthesized by reacting styrenated phenol and ethylene oxide under a salt mechanical homogeneous catalyst. However, when a salt-homogenizing catalyst is used, it is difficult to separate the catalyst and the product after the reaction, and a neutralization process is additionally required. Further, there is a disadvantage that a high-pressure reaction device capable of quantitatively supplying and controlling ethylene oxide as a reactant is required.

Therefore, there is a need for a new method for synthesizing styrenated phenol alkoxylates, specifically, alkylene oxide addition styrenated phenols as in the present invention, under mild reaction conditions, without using a high pressure reactor.

Chinese patent application publication CN102875799A (2013.01.16)

It is an object of the present invention to provide a process for producing an alkylene oxide addition styrenated phenol capable of quantitatively and precisely controlling an oxyalkylene group repeating unit bonded to styrenated phenol in the synthesis of an alkylene oxide addition styrenated phenol .

It is also an object of the present invention to provide a process for preparing an alkylene oxide addition styrenated phenol which is easy to handle reactants and does not require a high pressure reaction device for the supply and control of reactants.

It is another object of the present invention to provide a process for producing an alkylene oxide-added styrenated phenol which is easy to separate the catalyst in the reaction process and does not require a neutralization step after the reaction depending on the use of the catalyst.

The method for producing an alkylene oxide addition styrenated phenol of the present invention comprises reacting a styrenated phenol derivative with a cyclic alkylene carbonate under a basic metal catalyst to prepare an alkylene oxide addition styrenated phenol.

In one embodiment of the present invention, the styrenated phenol derivative may be represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ and R ₂ are independently hydrogen, halogen, (C1-C5) alkyl or (C1-C5) may be an alkoxy group, R ₃ is hydrogen, (C1-C5) alkyl or (C1- each other C5) alkoxy, a may be an integer of 1 to 3, x may be an integer of 0 to 5-a, and when x is 2 or more, R ₁ may be different from or the same as each other and y is 0 to 5 And when y is 2 or more, R < ₂ > may be different from or the same as each other.

In one example of the present invention, the cyclic alkylene carbonate may be used in an amount of 0.5 to 50 moles relative to 1 mole of the styrenated phenol derivative.

In one example of the present invention, the alkylene oxide-added styrenated phenol may be represented by the following general formula (2).

(2)

In Formula 2, R ₁ and R ₂ are independently hydrogen, halogen, (C1-C5) alkyl or (C1-C5) may be an alkoxy group, R ₃ is hydrogen, (C1-C5) alkyl or (C1- each other C5) alkoxy, a may be an integer of 1 to 3, x may be an integer of 0 to 5-a, and when x is 2 or more, R ₁ may be different from or the same as each other and y is 0 to 5 And when n is 2 or more, R ₂ may be the same or different from each other, and n and m may be independently an integer of 0 or more, and n and m are not 0 at the same time.

In one embodiment of the present invention, the cyclic alkylene carbonate may be used in an amount of 1 to 30 moles per mole of the styrenated phenol derivative in ethylene carbonate, and the alkylene oxide added styrenated phenol may be represented by the formula 2, In Formula 2, m may be 0, and n may be 1 to 15.

In one embodiment of the present invention, the basic metal catalyst comprises a carrier; And an alkali metal or a hydroxide thereof supported on the carrier.

In one embodiment of the present invention, the support may include one or more selected from MgO, CaO, SiO ₂ , AlCl ₃ , Al ₂ O ₃ , La ₂ O ₃ , ZrO ₂ and V ₂ O ₅ have.

In one embodiment of the present invention, the basic metal catalyst is an alkali metal or a hydroxide thereof; a carrier; And a dispersion medium; and then, the alkali metal or its hydroxide is supported on the carrier by heat treatment.

In one embodiment of the present invention, the heat treatment may be performed at 200 to 800 ° C.

The method for preparing an alkylene oxide addition styrenated phenol according to an exemplary embodiment of the present invention includes separating and removing a basic metal catalyst from an alkylene oxide addition styrenated phenol by centrifuging the mixture containing the product according to the reaction .

In one embodiment of the present invention, the reaction may be carried out at 60 to 200 ° C.

The alkylene oxide addition method of the present invention is characterized in that cyclic alkylene carbonate is used as a reactant for the alkylene oxide addition so that the repeating unit of the oxyalkylene group bonded to the styrenated phenol can be controlled quantitatively and precisely There is an effect.

Further, in the process for producing an alkylene oxide addition styrenated phenol according to the present invention, a cyclic alkylene carbonate is used as a reactant for addition of an alkylene oxide, thereby facilitating the handling of reactants and a high-pressure reaction apparatus for supplying and controlling reactants And to provide a process for producing an alkylene oxide addition styrenated phenol which is not required.

Further, the method of the present invention for producing an alkylene oxide addition styrenated phenol is advantageous in that a basic metal supported catalyst is used so that the catalyst can be easily separated in the reaction process and a neutralization process after the reaction depending on the use of the catalyst is not required.

Even if the effects are not explicitly mentioned in the present invention, the effects described in the specification anticipated by the technical features of the present invention and their inherent effects are treated as described in the specification of the present invention.

1 is a GPC spectrum of the substance obtained in Example 1, which was measured using Gel Permeation Chromatography (GPC).
2 is a GPC spectrum of a substance obtained in Example 2, which was measured using Gel Permeation Chromatography (GPC).
3 is a GPC spectrum of the substance obtained in Example 3 measured by Gel Permeation Chromatography (GPC).
4 is a GPC spectrum of the substance obtained in Example 4 measured by Gel Permeation Chromatography (GPC).
5 is a GPC spectrum of a substance obtained in Example 5 measured by Gel Permeation Chromatography (GPC).
6 is a graph showing an oxyalkylene group repeating unit bonded to a synthesized substance according to the number of moles of ethylene carbonate relative to 1 mole of a phenolic mixture in synthesis of the material obtained in Examples 1 to 6. Fig.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.

The drawings described in the present invention are provided by way of example so that a person skilled in the art can sufficiently convey the idea of the present invention. Therefore, the present invention is not limited to the illustrated drawings, but may be embodied in other forms, and the drawings may be exaggerated in order to clarify the spirit of the present invention.

In addition, unless otherwise defined, technical terms and scientific terms used in the present invention have the same meanings as those of ordinary skill in the art to which the present invention belongs. In the following description and the accompanying drawings, Description of known functions and configurations that may unnecessarily obscure the subject matter will be omitted.

Also, the singular form of the term used in the present invention can be construed as including plural forms unless otherwise indicated.

Also, units of% used unclearly in the present invention means weight percent.

Also, the substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described in this invention can include both linear, branched, or cyclic forms and can contain from 1 to 7 carbon atoms, preferably from 1 to 5 Carbon atoms, more preferably 1 to 3 carbon atoms.

The method for producing an alkylene oxide addition styrenated phenol of the present invention comprises reacting a styrenated phenol derivative with a cyclic alkylene carbonate under a basic metal catalyst to prepare an alkylene oxide addition styrenated phenol.

The styrenated phenol derivative may be any compound capable of producing styrenated phenol with addition of an alkylene oxide by reacting with a cyclic alkylene carbonate, for example, a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ and R ₂ are independently hydrogen, halogen, (C1-C5) alkyl or (C1-C5) may be an alkoxy group, R ₃ is hydrogen, (C1-C5) alkyl or (C1- each other C5) alkoxy. a may be an integer of 1 to 3, x may be an integer of 0 to 5-a, and when x is 2 or more, R ₁ may be different from or the same as each other. y may be an integer of 0 to 5, and when y is 2 or more, R ₂ may be the same or different from each other.

According to one embodiment of the present invention, R ₁ and R ₂ in Formula (1) are preferably independently of one another halogen, (C 1 -C 3) alkyl or (C 1 -C 3) alkoxy, Otherwise x or y can be zero.

The styrenated phenol derivative may be used in a state where various styrenated phenol derivatives are mixed. As a specific example, the styrenated phenol derivative may be any one or two selected from among a monostyrenated phenol derivative represented by the general formula (1) in which a is 1, a di-styrenated phenol derivative having a = 2, and a tristyrenated phenol derivative having a = 3 Or more. Preferably, at least 60 mol% or more of the di-styrenated phenol derivative or the di-styrenated phenol derivative is contained.

In the production process of the present invention, the alkylene oxide addition styrenated phenol synthesized by reacting the styrenated phenol derivative with the cyclic alkylene carbonate is styrenated phenol having an oxyalkylene group repeating unit. Specifically, when any one or two or more selected from cyclic alkylene carbonate such as ethylene carbonate and propylene carbonate is used, the alkylene oxide addition styrenated phenol to be synthesized may be any one or two selected from oxyethylene group, Or more of the oxyalkylene group repeating units.

As a specific example, when the styrenated phenol derivative represented by Formula 1 is used as a reactant in the production method of the present invention, an alkylene oxide addition styrenated phenol represented by Formula 2 below may be synthesized.

(2)

In Formula 2, R ₁ and R ₂ are independently hydrogen, halogen, (C1-C5) alkyl or (C1-C5) may be an alkoxy group, R ₃ is hydrogen, (C1-C5) alkyl or (C1- each other C5) alkoxy. a may be an integer of 1 to 3, x may be an integer of 0 to 5-a, and when x is 2 or more, R ₁ may be different from or the same as each other. y may be an integer of 0 to 5, and when y is 2 or more, R ₂ may be different from or the same as each other. n and m may independently be an integer of 0 or more, and n and m are not 0 at the same time.

As a specific example, in the production process of the present invention, when ethylene carbonate is used as the cyclic alkylene carbonate, the alkylene oxide addition styrenated phenol to be synthesized may be an ethylene oxide addition styrenated phenol. The ethylene oxide addition styrenated phenol may be represented by the following general formula (3).

(3)

As a specific example, in the production process of the present invention, when propylene carbonate is used as the cyclic alkylene carbonate, the alkylene oxide addition styrenated phenol to be synthesized may be propylene oxide addition styrenated phenol. The propylene oxide addition styrenated phenol may be represented by the following general formula (4).

[Chemical Formula 4]

In Formula 3 or Formula 4, R ₁ and R ₂ may be independently hydrogen, halogen, (C1-C5) alkyl or (C1-C5) alkoxy each other, R ₃ is hydrogen, (C1-C5) alkyl Or (C1-C5) alkoxy. a may be an integer of 1 to 3, x may be an integer of 0 to 5-a, and when x is 2 or more, R ₁ may be different from or the same as each other. y may be an integer of 0 to 5, and when y is 2 or more, R ₂ may be different from or the same as each other. In Formula 3, n may be an integer of 0 or more, and in Formula 4, m may be an integer of 0 or more.

In the present invention, the cyclic alkylene carbonate may be used in an amount of 0.5 to 50 mol, specifically 1 to 30 mol, per mol of the styrenated phenol derivative.

In the present invention, by controlling the molar ratio of the styrene-phenol derivative and the cyclic alkylene carbonate, the oxyalkylene repeating unit of the synthesized alkylene oxide-added styrenated phenol can be controlled. For this purpose, It is very good that ethylene carbonate is used as the alkylene carbonate. For example, in the case where the alkylene oxide addition moiety represented by the formula (2) is produced, the number of n in the formula (3) can be selectively and precisely controlled.

In a preferred embodiment of the present invention, when ethylene oxide addition styrenated phenol represented by Formula 3 is used, ethylene carbonate is used in an amount of 1 to 30 moles relative to 1 mole of styrenated phenol derivative, An ethylene oxide addition styrenated phenol can be prepared.

Also, when ethylene carbonate is used in an amount of 1 to 10 moles per mole of the styrenated phenol derivative, an ethylene oxide addition styrenated phenol having a low dispersion degree of 1.5 or less, specifically 1.2 to 1.5, can be prepared, and 12 to 14 moles , It is possible to prepare an ethylene oxide addition styrenated phenol having a relatively low dispersion degree of 1.85 or less, specifically 1.60 to 1.85.

For the production of an ethylene oxide addition styrenated phenol having an appropriate oxyethylene group repeating unit of 5 to 14 as a nonionic surfactant, ethylene carbonate may be used in an amount of 10 to 20 moles relative to 1 mole of the styrenated phenol derivative.

The basic metal catalyst may be an alkali metal or hydroxide thereof; And a carrier on which the alkali metal or its hydroxide is supported.

The alkali metal may include one or more selected from among alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as magnesium and calcium. However, it should be understood that the present invention is not limited thereto.

In one example of the present invention, the carrier may be an oxide of a transition metal or a chloride of a transition metal. Specifically, the support may include any one or two or more selected from MgO, CaO, SiO ₂ , AlCl ₃ , Al ₂ O ₃ , La ₂ O ₃ , ZrO ₂ and V ₂ O ₅ . In addition, the carrier may be a carrier having a three-dimensional skeleton structure having pores such as zeolite. The carrier may be in the form of particles and may have an average particle size of 5 to 500 μm. However, this is a preferred example, and the present invention is not limited thereto.

In the present invention, specific examples of the reaction of a styrenated phenol derivative and a cyclic alkylene carbonate with a cyclic alkylene carbonate include introducing a styrenated phenol derivative and a cyclic alkylene carbonate into an inert gas atmosphere such as argon gas, And then adjusting the temperature to adjust the alkylene oxide addition to the styrenated phenol.

In the present invention, when the styrenated phenol derivative and the cyclic alkylene carbonate are reacted with each other under a basic metal catalyst, the reaction temperature and the reaction time may be such that the reaction can sufficiently proceed. For example, the reaction temperature may be 60 to 200 ° C, specifically 150 to 190 ° C, and the reaction time may be 3 to 48 hours, specifically, 6 to 24 hours. However, the present invention is not limited thereto. Of course.

In the present invention, since a basic metal supported catalyst different from the conventional salt mechanical uniform catalyst is used, it is easy to separate the catalyst in the reaction process and a complicated post-treatment process such as a neutralization process for removing unreacted catalyst is not required There are advantages.

The method for preparing an alkylene oxide addition styrenated phenol according to an embodiment of the present invention is characterized in that after the reaction is completed, the mixture containing the product according to the reaction is centrifuged to separate the basic metal catalyst from the alkylene oxide addition styrenated phenol And a step of removing the magnetic field. At this time, a diluting solvent such as acetone may be added to the mixture to effectively separate the alkylene oxide added styrenated phenol from the basic metal catalyst.

The basic metal catalyst may be a hydroxide of an alkali metal; carrier; And a dispersion medium; and carrying the alkali metal or its hydroxide on the carrier by heat treating the mixture. At this time, the dispersion medium is not limited as long as the alkali metal or its hydroxide can be dissolved and the carrier can be dispersed. Examples thereof include water, tetrahydrofuran, nucleic acid and the like.

In the preparation of the basic metal catalyst, a hydroxide of an alkali metal; carrier; And the dispersion medium may contain 1 to 80 parts by weight, specifically 10 to 60 parts by weight, of the alkali metal hydroxide per 100 parts by weight of the dispersion medium, and 20 to 200 parts by weight of the carrier, specifically 30 to 100 parts by weight Section. However, it should be understood that the present invention is not limited thereto.

The heat treatment may be performed so long as it can be sufficiently baked that the catalyst can be activated. Specifically, the heat treatment temperature may be 200 to 800 ° C., preferably 400 to 600 ° C., and the heat treatment time may be 2 to 24 hours, but this is a preferred example, but the present invention is not limited thereto.

In the preparation of the basic metal catalyst, a hydroxide of an alkali metal; carrier; And a dispersion medium; and before the heat treatment of the mixed mixture is performed, removing the dispersion medium. It is possible to accelerate the activation of the catalyst in which the heat treatment is carried out at a firing temperature of 200 ° C or more in the state where there is no dispersion medium such as water.

Specifically, removal of the dispersion medium can be exemplified by drying in which the dispersion medium is removed by evaporation. The drying temperature may be higher than the temperature at which the dispersion medium evaporates. Such as the boiling point of the dispersion medium to 200 ° C. The drying time may be as long as the dispersion medium is sufficiently evaporated, for example, 12 to 24 hours. However, it should be understood that the present invention is not limited thereto.

The alkylene oxide addition styrenated phenol prepared by the process of the present invention can be used as a nonionic surfactant and can be used in the production of display materials such as active matrix organic light And can be applied to various technical fields such as a color filter for a LCD panel and a developer for a thin film transistor, which are key components in manufacturing a flexible-AMOLED (Flexible-AMOLED) have.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is described in more detail with reference to the following Examples. However, the scope of the present invention is not limited by the following Examples.

Preparation of basic metal supported catalyst

10.0 g of lanthanum oxide (La ₂ O ₃ ) was added to a Schlenk tube, and then a 30% by weight aqueous potassium hydroxide solution in which potassium hydroxide (KOH) 6.0 g was dissolved in 20 ml of distilled water was added to the Schlenk tube And further stirred for 3 hours.

Thereafter, the catalyst was dried at 150 ° C. for 24 hours to remove moisture, and then calcined at 600 ° C. for 6 hours to prepare a catalyst (KOH / La ₂ O ₃ ) having catalytic activity.

Ethylene oxide  addition Styrenization  Synthesis of phenol

After replacing the air inside the 200 cc Schlenk tube with argon, the styrenated phenol represented by the following formula (5), the styrenated phenol represented by the following formula (6) and the styrenated phenol represented by the following formula (7) were changed to 13.8: 72.1: 14.1 (3.024 g, 10 mmol) in a molar ratio of < RTI ID = 0.0 > Ethylenecarbonate (0.8806 g, 10 mmol); And the above basic metal supported catalyst (0.1952 g, 5 wt%) were added into the Schlenk tube and stirred at 170 캜 for 24 hours.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

After stirring was completed, the reaction mixture was cooled, added with acetone, stirred for 10 minutes, and then centrifuged at 3,500 rpm. A brown liquid material with a viscosity of vacuum, i. E., A synthetic ethylene oxide addition styrenated phenol, was obtained by taking the transparent brown supernatant of the centrifuged mixture.

Example 1 was repeated except that the content of ethylene carbonate in Example 1 was 50 mmol, that is, the equivalent ratio between the styrenated phenol mixture and ethylene carbonate was 1: 5.

The procedure of Example 1 was repeated except that the content of ethylene carbonate in Example 1 was 120 mmol, that is, the equivalent ratio between the styrenated phenol mixture and ethylene carbonate was 1:12.

Example 1 was repeated except that the content of ethylene carbonate in Example 1 was 140 mmol, that is, the equivalent ratio of styrenated phenol mixture to ethylene carbonate was 1:14.

The procedure of Example 1 was repeated except that the content of ethylene carbonate in Example 1 was 300 mmol, that is, the equivalent ratio between the styrenated phenol mixture and ethylene carbonate was 1:30.

For the analysis of the materials obtained in Examples 1 to 5, the molecular weight was measured under the conditions shown in Table 1 below using Gel Permeation Chromatography (GPC), and it was measured from Examples 1 to 5 One GPC spectrum is shown in Figures 1 to 5, respectively.

Column TSKgel HXL-type columns (7.8 mm x 300 cm x 3) Mobile phase THF (tetrahydrofuran) Flow rate 1 ml / min Detection UV (254 nm) Temperature 40 ℃ Injection volume 20 μl

As a result, it was confirmed that the compounds represented by the following formula (3) were present in all cases of Examples 1 to 5.

(3)

Using the GPC measurement data, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the dispersion degree (Mw) of the phenol based mixture and the ethylene carbonate in the synthesis of the materials obtained in Examples 1 to 5 / Mn) and an oxyethylene group repeating unit (n in the above formula (3)) are shown in Table 2 below.

Phenol-based mixture: molar ratio of ethylene carbonate Mw Mn Mw / Mn n Example 1 1: 1 351 245 1.4335 One Example 2 1: 5 381 258 1.4760 2 Example 3 1:12 627 347 1.8048 7 Example 4 1:14 876 479 1.8309 13 Example 5 1:30 972 409 2.3782 15

In Table 2, n in the formula (3) as an oxyethylene group repeating unit is an average value, and the average molecular weight of the material obtained in each example is measured using GPC, and the value obtained by subtracting the molecular weight of the formula (6) from the average molecular weight The molecular weight of the oxyethylene group was divided to calculate n.

In the case of Example 1 and Example 2 in which the molar ratio of the phenol-based mixture and ethylene carbonate was 1: 1 to 5, the dispersion degree was excellent at 1.5 or less, and the molar ratio of the phenol-based mixture to ethylene carbonate was 1: In the case of Example 3 and Example 4 which were synthesized with 14, the dispersion degree was 1.85 or less, which is relatively good.

Further, FIG. 6 graphically shows the oxyethylene group repeating unit of the synthesized substance based on the molar amount of ethylene carbonate with respect to 1 mole of the phenol-based mixture based on the data of Table 2.

From this, it can be seen that by controlling the molar equivalent of the cyclic alkylene carbonate to the phenol-based mixture, the alkylene oxide addition can control the repeating unit of the oxyalkylene group of the addition-styrenated phenol and control more precisely . That is, it can be seen that the molecular weight of the ethylene oxide added styrenated phenol can be selectively and precisely controlled through the production method of the present invention.

In addition, ethylene oxide, which is a reactant generally used in the synthesis of conventional styrenated phenol alkoxylates, is explosive and difficult to handle, whereas in the present invention, solid ethylene carbonate is used as the reactant, thereby ensuring process stability. Also, since a high-pressure reaction device, which is essential for the supply and control of ethylene oxide, is not required, the process can be simplified, and the cost reduction effect of the process is also excellent.

In addition, in the case of the liquid catalyst used in the synthesis of the conventional styrenated phenol alkoxylate, a step of neutralizing the unreacted catalyst and a step of removing the salt generated in the neutralization step were essentially involved, while in the present invention, The removal of the catalyst was very easy.

Claims (10)

Reacting a styrenated phenol derivative represented by the following formula (1) with a cyclic alkylene carbonate under a basic metal catalyst to prepare an alkylene oxide-added styrenated phenol; and
Separating and removing the basic metal catalyst from the alkylene oxide addition styrenated phenol by centrifuging the mixture comprising the product according to the reaction
/ RTI >
Wherein the basic metal catalyst is prepared by heat treating a mixture of an alkaline metal or a hydroxide thereof and a carrier to support the alkaline metal or its hydroxide on a carrier to produce an alkylene oxide adduct of styrenated phenol.
[Chemical Formula 1]

[In the above formula (1)
R ₁ and R ₂ are independently from each other hydrogen, halogen, (C 1 -C 5) alkyl or (C 1 -C 5)
R ₃ is hydrogen, (C 1 -C 5) alkyl or (C 1 -C 5) alkoxy,
a is an integer of 1 to 3,
x is an integer of 0 to 5-a, and when x is 2 or more, R < _{1 >} may be different from or the same as each other,
y is an integer of 0 to 5, and when y is 2 or more, R ₂ may be the same or different from each other] delete The method according to claim 1,
Wherein the cyclic alkylene carbonate is used in an amount of 1 to 50 moles relative to 1 mole of the styrenated phenol derivative. The method according to claim 1,
Wherein the alkylene oxide addition styrenated phenol is represented by the following formula (2).
(2)

[In the formula (2)
R ₁ and R ₂ are independently from each other hydrogen, halogen, (C 1 -C 5) alkyl or (C 1 -C 5)
R ₃ is hydrogen, (C 1 -C 5) alkyl or (C 1 -C 5) alkoxy,
a is an integer of 1 to 3,
x is an integer of 0 to 5-a, and when x is 2 or more, R < _{1 >} may be different from or the same as each other,
y is an integer of 0 to 5, and when y is 2 or more, R ₂ may be the same or different from each other,
n and m are independently an integer of 0 or more, and n and m are not 0 at the same time] 5. The method of claim 4,
The cyclic alkylene carbonate is ethylene carbonate, used in an amount of 1 to 30 moles per mole of the styrenated phenol derivative,
Wherein m is 0 and n is 1 to 15, in the formula (2). The method according to claim 1,
The basic metal catalyst comprises a carrier; And an alkali metal or hydroxide thereof supported on the carrier,
The carrier may be at least one selected from the group consisting of alkylene oxide addition styrenated phenol comprising at least one selected from MgO, CaO, SiO ₂ , AlCl ₃ , Al ₂ O ₃ , La ₂ O ₃ , ZrO ₂ and V ₂ O ₅ Way. The method according to claim 6,
The basic metal catalyst may be an alkali metal or hydroxide thereof; carrier; And a dispersion medium; and carrying the alkali metal or its hydroxide on the carrier by heat treating the mixed mixture. 8. The method of claim 7,
Wherein the heat treatment is performed at 200 to 800 ° C. delete The method according to claim 1,
Wherein the reaction is carried out at 60 to 200 占 폚.

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