KR101821799B1 - Method of preparing for selective di-styrenated phenol using zirconium oxide solid acid catalyst manufactured by being impregnated zirconium hydroxide in sulfuric acid aqueous solution - Google Patents

Abstract

The present invention relates to a selective preparation method of di-styrenated phenol represented by chemical formula 1 obtained by making a phenol compound represented by chemical formula 2 react with a styrene monomer in the presence of a zirconium oxide solid acid catalyst prepared by impregnating zirconium hydroxide with an aqueous sulfuric acid solution. In chemical formulas 1 and 2, R_1 and R_2 are each independently selected from hydrogen, a C_1-C_20 alkyl group, a C_1-C_20 alkoxyl group, a C_3-C_30 cycloalkyl group, and a C_6-C_30 aryl group. The selective preparation method according to the present invention can minimize the amount of an unreacted residual material and can dramatically increase selectivity of di-styrenated phenol by exhibiting a high reactivity in the presence of the zirconium oxide solid acid catalyst prepared by impregnating zirconium hydroxide with the aqueous sulfuric acid solution.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for selectively producing a di-styrene-substituted phenol using a zirconium oxide solid acid catalyst prepared by impregnating zirconium hydroxide with an aqueous solution of sulfuric acid. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zirconium oxide solid- ACID AQUEOUS SOLUTION}

More particularly, the present invention relates to a process for selectively producing di-styrene nitrile phenol, and more particularly, to a process for selectively producing di-styrene nitrile phenol using a zirconium oxide solid acid catalyst prepared by impregnating zirconium hydroxide with an aqueous solution of sulfuric acid, To a process for producing nated phenol in high yield.

Plastics are widely used not only for industrial purposes but also for everyday life due to their excellent chemical and physical properties. Such a plastic is rarely used as such, and a small amount of an additive is added to the raw material in accordance with the intended use to supplement its characteristics. Typical examples thereof include an antioxidant to increase the oxidation stability of the raw material . The antioxidant functions to stabilize the plastic by reacting with radicals generated by the oxidation reaction of heat, oxygen, light and the like in the plastic. The antioxidant releases its own hydrogen to stabilize the radical, which itself becomes a radical, which remains in a stable form through a resonance effect or electron rearrangement.

Typical examples of the antioxidant include amine-based antioxidants and phenol-based antioxidants. Particularly, phenol-based antioxidants have excellent thermal stability and are widely used as non-staining antioxidants, unlike amine-based antioxidants.

Typical examples of phenolic antioxidants are styrenated phenols (SPs), in which the phenol and styrene are alkylated to replace the phenol hydrogen with styrene. In general, when styrene is used in an amount of 2 equivalents to phenol, mono-styrenated phenol (MSP), di-styrenated phenol (DSP) in which two styrenes are bonded, and styrene Tri-styrenated phenol (TSP) compound is produced in a weight ratio of MSP: DSP: TSP = 10: 15: 30 to 45: 35: 45, and the unreacted residual phenol There is a problem that an excessive amount of styrene remains.

In Korean Patent No. 10-1111248, styrene-naphthyl phenol is synthesized using a liquid acid catalyst as a homogeneous catalyst. Liquid acid catalysts such as sulfuric acid, nitric acid, phosphoric acid and the like can produce stainned phenol products and cause discoloration due to the violent reaction conditions of high temperature and strong acid, low selectivity, sensitivity to moisture, There is a problem that the reproducibility is low depending on the kind of the substance and the amount of catalyst used. Further, since the catalyst can not be reused and separation of the product from the catalyst is not easy, it can act as an impurity, and therefore a search for a new heterogeneous catalyst is required.

Further, it has been difficult to selectively produce any one of the conventional styrenated phenols, and further complicated separation processes must be performed to separate the catalyst and the product. Among them, di-styrenated phenol can be applied not only as an antioxidant but also as a surfactant because it can act as a hydrophobic part of a surfactant. Thus, mono-styrenated phenol having low stability as a surfactant and tri - Production of styrenated phenol has a minimum content, and a method for increasing the degree of di-styrenated selectivity is needed.

Korean Patent No. 10-1111248

The present invention provides a method for selectively producing di-styrenated phenol which is excellent in thermal stability and discoloration stability and capable of selectively producing di-styrenated phenol in order to solve the problems of the conventional production method described above .

The present invention also provides a simple and economical production process which minimizes the unreacted residual materials, reduces the content of mono-styrenated phenol and tri-styrenated phenol and improves the selectivity of the di- - < / RTI > a process for the selective preparation of styrene-substituted phenols.

The present invention relates to a process for the selective preparation of di-styrenated phenol represented by the following formula (1) wherein a phenol compound represented by the following formula (2) is reacted with a styrene monomer under a zirconium oxide solid acid catalyst prepared by impregnating zirconium hydroxide with an aqueous solution of sulfuric acid Lt; / RTI >

[Chemical Formula 1]

(2)

(In the above Formulas 1 to 2,

R ₁ and R ₂ are each independently selected from hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, a C ₃ -C ₃₀ cycloalkyl group, and a C ₆ -C ₃₀ aryl group.

The zirconium oxide solid acid catalyst may have a crystal structure in which a monoclinic system and a tetragonal system are mixed.

The crystal structure may be a mixture of a tetragonal system and a monoclinic system having a peak intensity ratio of 40:60 to 70:30 when measured by X-ray diffraction (XRD) analysis.

The zirconium oxide solid acid catalyst may be one containing 3 to 6% by weight of sulfate ions based on the total weight of the zirconium hydroxide particles and the aqueous sulfuric acid solution.

The zirconium oxide solid acid catalyst may be one in which sulfuric acid ions are attached to zirconium hydroxide particles.

The zirconium hydroxide particles may have an average particle diameter of 10 to 50 mu m.

The styrene monomer may contain 1 to 3 mol based on 1 mol of the phenol compound.

The zirconium oxide solid acid catalyst may contain 3 to 6 wt% based on the mixture of the phenolic compound and the styrene monomer.

The reaction of the phenolic compound and the styrene monomer may be carried out at a reaction temperature of 50 to 170 ° C.

The mixture of the phenolic compound and the styrene monomer may be reacted under an inert gas supply of argon, nitrogen, helium or neon.

The process for the selective preparation of di-styrene-substituted phenol according to the present invention shows a high reactivity under a zirconium oxide solid acid catalyst prepared by impregnating zirconium hydroxide with an aqueous solution of sulfuric acid, thereby minimizing the amount of unreacted residual materials. The selectivity of the styrene-substituted phenol can be remarkably increased.

In addition, the process for selectively producing di-styrene-substituted phenol according to the present invention can be carried out by a simple process, thereby increasing the industrial efficiency and enabling mass production at a lower cost.

1 is an XRD result showing a crystal structure of a catalyst according to an embodiment of the present invention. _{(A1) ZrO 2 (Tetragonal,} from ICSD), (A2) ZrO 2 (Monoclinic, from ICSD), (B) Pure ZrO 2, (C) 15-SO 4 2- / ZrO 2, (D) 10-SO ^{_{4 2- / ZrO 2, (E}} ) 7-SO 4 2- / ZrO 2, (F) 5-SO 4 2- / ZrO 2, (G) 3-SO 4 2- / ZrO 2, (H) 5 -SO ₄ ^2- / ZrO ₂ (dried), (I) Pure Zr (OH) ₄ .
FIG. 2 shows the results of the conversion of phenolic compounds and styrene monomers and the selectivity of styrene-based phenols according to the sulfate ion concentration in an aqueous sulfuric acid solution of the present invention.
FIG. 3 shows results of conversion of phenol compounds and styrene monomers and selectivity of styrene-based phenols according to the catalyst content of the examples of the present invention.
4 shows the results of the conversion of the phenolic compound and the styrene monomer and the selectivity of the styrene-based phenol according to the reaction temperature contents of the examples of the present invention.

Hereinafter, a method for selectively producing di-styrene-based phenol using zirconium oxide solid acid catalyst prepared by impregnating zirconium hydroxide according to the present invention with an aqueous sulfuric acid solution will be described in more detail. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In the present specification, "N-SO ₄ ^2- / ZrO ₂ " (wherein N is an integer selected from 1 to 20, and the unit is wt%) is a zirconium oxide solid acid catalyst prepared by impregnating zirconium hydroxide in an aqueous sulfuric acid solution Means the sulfate ion concentration of the aqueous sulfuric acid solution impregnated with the zirconium hydroxide, and the concentration is calculated by calculating the sulfate ion content of the zirconium hydroxide particles.

The present invention relates to a method for producing styrene-substituted phenol, which comprises reacting phenol with a styrene monomer to simultaneously produce mono-, di-, and tri- styrenated phenols as shown in Reaction Scheme 1 . However, it has been difficult to selectively produce any one of the conventional styrenated phenols, and further complicated separation processes must be performed to separate the catalyst and the product.

In addition, styrene-substituted phenols containing conventional discoloration and impurities or unreacted residual materials may be used only as antioxidants, but the present invention is directed to a process wherein the oxidation of the present invention with a simple process while minimizing the amount of unreacted residual material The present invention has been devised to provide a novel method for selectively producing di-styrenated phenol which can be applied as a surfactant, as well as an agent for inhibiting the hydrophobicity of a surfactant.

[Reaction Scheme 1]

The present invention will be described in detail,

The present invention relates to a process for the selective preparation of di-styrenated phenol represented by the following formula (1) wherein a phenol compound represented by the following formula (2) is reacted with a styrene monomer under a zirconium oxide solid acid catalyst prepared by impregnating zirconium hydroxide with an aqueous solution of sulfuric acid Lt; / RTI >

[Chemical Formula 1]

(2)

(In the above Formulas 1 to 2,

R ₁ and R ₂ are each independently selected from hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, a C ₃ -C ₃₀ cycloalkyl group, and a C ₆ -C ₃₀ aryl group.

Substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in the present invention include both straight chain and branched forms. &Quot; Cycloalkyl ", alone or as part of another group described in the present invention, refers to a fully saturated and partially unsaturated hydrocarbon ring of three or more carbon atoms, including where the aryl or heteroaryl is fused .

The term " aryl " as used in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination, in which each ring is optionally substituted by a single or a plurality of ring atoms, preferably containing from 4 to 7, preferably 5 or 6, A fused ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples thereof include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, But is not limited thereto.

For example, R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, Butyl, n-pentyl, i-pentyl, s-pentyl, n-hexyl, i-hexyl, s-hexyl, phenyl, naphthyl and biphenyl.

More preferably the phenolic compound of formula (2) is selected from the group consisting of phenol, m-cresol, p-cresol, o-cresol, 2,5-xylenol, 3,5-xylenol, 3,4- Ethylphenol, p-ethylphenol, on-propylphenol, mn-propylphenol, pn-propylphenol, o-propylphenol, butylphenol, m-butylphenol, pn-butylphenol, o-butylphenol, mi-butylphenol, , m-butylphenol, pt-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxyphenol, Butoxyphenol, p-phenoxyphenol, m-propoxyphenol, p-propoxyphenol, o-butoxyphenol, m-butoxyphenol, p-butoxyphenol and the like.

The zirconium oxide solid acid catalyst prepared by impregnating the zirconium hydroxide with sulfuric acid aqueous solution as proposed in the present invention can be used for the phenolic compound and the styrene monomer to react with the phenolic compound and the styrene monomer, It is possible to obtain an effect of maximizing the yield and purity of phenol (DSP), and to suppress the production of mono-styrene-naphthol phenol (MSP) and tri-styrene-naphthol phenol (TSP) as polymerized by-products as much as possible. Therefore, the present invention does not use a polymerization terminator that is used for the purpose of inhibiting the production of the polymerization by-product, and therefore, the purification process due to coloring is not performed, and thus, the process simplification effect can be expected.

Further, the zirconium oxide solid acid catalyst is characterized by being a solid acid catalyst. Conventionally, the use of a liquid acid catalyst in the production of styrenated phenols can significantly shorten the reaction time, unlike the case where a long reaction time is required. In addition, the liquid acid catalyst was forced to generate waste acid and wastewater. However, by using the solid acid catalyst, it is possible to recover the catalyst through a simple filtration process without discharging waste acid and wastewater.

The zirconium oxide solid acid catalyst (SO ₄ ^2- / ZrO ₂ ) of the present invention can be produced by impregnating zirconium hydroxide (Zr (OH) ₄ ) particles with an aqueous solution of sulfuric acid and impregnating sulfate ions to zirconium hydroxide particles.

The zirconium hydroxide particles of the present invention may serve as a carrier for dispersing and retaining an active material having a catalytic function in a stable manner. Although the carrier is not active, when the catalyst is prepared using only the active material having low thermal stability, the surface area of the active material can be greatly reduced by sintering during the reaction. Accordingly, if the active material is supported on a carrier having excellent thermal stability, the carrier can be stabilized, and the catalyst deactivation due to sintering can be suppressed. In addition, the carrier may increase the mechanical stability of the catalyst, so that the catalyst can be conveniently used to form a suitable catalyst.

Therefore, the zirconium hydroxide zirconium hydroxide particles are very strong in interaction with the active material as the support, so that the zirconium hydroxide solid acid catalyst in which the sulfate ion is impregnated can be used as a catalyst having a higher activity than that of 100% sulfuric acid and having high activity, Chemically stable, and easy to handle without causing pollution.

The zirconium oxide solid acid catalyst of the present invention may be prepared by adding 3 to 6% by weight of sulfate ions to the total weight of the zirconium hydroxide particles and the aqueous sulfuric acid solution. When zirconium hydroxide is impregnated with an aqueous sulfuric acid solution containing sulfuric acid ions within the above range, it may have a mixed crystal structure of a monoclinic system and a tetragonal system, and may have a high activity as an acid catalyst and a wide specific surface area. The selectivity of the nated phenol can be improved.

Fourier transform infrared spectroscopy (FT-IR, NicoletTM isTM 10, Thermo Scientific) analysis was performed to confirm the presence of sulfate ions (SO ₄ ^2- ) on the catalyst surface of the present invention. FT-IR spectrum of 1075㎝ ^- as in the ^first and 1202㎝ ^-1 indicated the asymmetric vibration absorption peaks due to the coupling bore OSO was found that SO ₄ ^2- ions are present on the catalyst surface. The change of the carrier due to the adhesion of the sulfate ion (SO ₄ ^2- ) was confirmed by X-ray diffraction (X-ray diffraction, X'pert ³ , MRD, PANalytical Netherlands).

According to one embodiment of the present invention, a zirconium oxide solid acid catalyst can be prepared by impregnating zirconium hydroxide particles into a sulfuric acid aqueous solution, which is a solution of an active material, as a carrier. Specifically, zirconium hydroxide particles may be impregnated with an aqueous sulfuric acid solution and stirred for 1 to 6 hours. It is preferable that sulfuric acid ions can be uniformly adhered during agitation within the above-mentioned period of time and the amount of impregnation can be easily controlled.

The zirconium hydroxide impregnated with the sulfate ion is filtered and dried at 100 to 150 ° C. for about 10 to 20 hours and then calcined in an electric furnace at 500 to 700 ° C. for 1 to 6 hours to prepare a zirconium oxide solid acid catalyst impregnated with sulfate ions can do.

The drying temperature is preferably from 100 to 150 ° C. because it affects the movement of the sulfate ions during the drying, so that the water is gradually evaporated to uniformly disperse the sulfate ions, and the sulfate ions can be sufficiently adhered to the zirconium hydroxide particles desirable.

The zirconium hydroxide does not have a pronounced acid basicity, but it can show a very strong acidity after being treated with sulfuric acid and then calcined. Since the zirconium hydroxide is in a solid state and its shape is fixed, it is difficult to separate and handle the reaction product when the liquid acid catalyst is used in the past, and it is possible to solve problems such as corrosion of the reaction vessel and disposal of the catalyst after the reaction is terminated.

The zirconium oxide solid oxide catalyst of the present invention may have a crystal structure in which monoclinic and tetragonal zirconium are mixed with each other to form a crystal structure while changing the structure of zirconium hydroxide to zirconium oxide by the above firing .

The crystal structure may be a mixture of a tetragonal system and a monoclinic system having a peak intensity ratio of 40:60 to 70:30 when measured by X-ray diffraction (XRD) analysis. When the amount of the zirconium oxide solid acid catalyst is within the above range, the reaction can be carried out under a condition that the sulfuric acid ion concentration of the sulfuric acid aqueous solution is low, which is a mild condition, and the selectivity of the di- desirable.

Since the zirconium oxide solid acid catalyst of the present invention is not used to prepare a zirconium oxide solid acid catalyst and the conventional zirconium oxide particles are used as a carrier and impregnated with an aqueous sulfuric acid solution to produce a zirconium oxide solid acid catalyst, Lt; / RTI > The crystal structure of the zirconium oxide particles varies depending on the temperature, and is monoclinic at less than 1170 ° C, tetragonal at 1170 to 2370 ° C, and cubic at 2370 ° C or higher.

The zirconium hydroxide particles may have an average particle size of 10 to 50 占 퐉, but the present invention is not limited thereto. The specific surface area of the zirconium hydroxide particles may be 10 to 100 m 2 / g, preferably 30 to 70 m 2 / g, but is not limited thereto.

When the zirconium hydroxide particles have a particle size and a specific surface area within the above range, the impregnation amount of the sulfate ion is increased, and the surface area is enlarged, thereby maximizing the operation capability as a catalytic active material.

According to one aspect of the present invention, there is provided a process for selectively producing di-styrene-substituted phenol, comprising the steps of: mixing a phenolic compound and a styrene monomer; performing an alkylation reaction under a zirconium oxide solid acid catalyst impregnated with a sulfate ion; And then selectively producing it.

The reaction mechanism for the alkylation of the phenolic compound of the present invention with the styrene monomer is shown in the following reaction formula (2).

[Reaction Scheme 2]

Specifically, the zirconium hydroxide is converted into zirconium oxide through firing after impregnating zirconium hydroxide with an aqueous solution of sulfuric acid, and sulfate ions are impregnated on the surface of the zirconium oxide solid acid catalyst as shown in the reaction formula (2). The sulfate ion strongly attracts the electrons of the zirconium oxide to lower the electron density of Zr. Zr with a lower electron density produces a strong Lewis acid point capable of receiving electron pairs. The phenolic compound and the styrene monomer are coordinated to the Lewis acid sites of the solid acid catalyst, and styrene-substituted phenols (SPs) can be produced by attacking the double bond of styrene which is rich in electrons in the H ⁺ of the Bststed acid.

According to one embodiment of the present invention, the styrene monomer may contain 1 to 3 moles based on 1 mole of the phenol compound. Preferably, the use of the styrene monomer in a molar ratio of 2 mol per 1 mol of the phenol compound is preferable because it can increase the selectivity of the di-styrenated phenol.

The di-styrenated phenol of the present invention has a molecular weight and viscosity corresponding to that between the mono-styrenated phenol and the tri-styrenated phenol, and the mono-styrenated phenol and the tri-styrenated phenol The present invention can be applied not only as an antioxidant but also as a hydrophobic component of a surfactant. Therefore, the present invention can provide an antioxidant, It has the advantage of being applicable as an activator.

The zirconium oxide solid acid catalyst of the present invention may contain 1 to 20 wt% based on the mixture of the phenolic compound and the styrene monomer. Preferably 3 to 7% by weight. When it is used in the above-mentioned range, the reaction time can be shortened as well as excellent reactivity.

The reaction conditions of the di-styrenated phenol according to an embodiment of the present invention will be specifically described. The reaction between the phenol compound and the styrene monomer is carried out at a reaction temperature of 50 to 170 ° C, preferably 60 to 120 ° C, But it is not limited thereto.

The reaction may be conducted for 1 to 6 hours, but is not limited thereto.

The product of the styrene-naphthyl phenol prepared by the above production method can be obtained by separately filtering it with a catalyst filter or the like without a solvent and an additional process.

Specifically, for example, the mixture of the phenolic compound and the styrene monomer may be reacted under an inert gas of argon, nitrogen, helium, or neon, , But is not limited thereto. When the reaction is carried out under the supply of the inert gas, it is preferable in terms of minimizing unreacted residual materials and reaction by-products.

According to the process for producing styrene-substituted phenol of the present invention, the ratio of di-styrenated phenol in the final product can be 50 to 70 mol% using zirconium oxide solid acid catalyst, and unreacted materials can be minimized .

The styrene-substituted phenol having a high content of di-styrene-substituted phenol prepared by the present invention can be applied not only to high-quality antioxidants such as synthetic rubbers and resins but also to raw materials for surfactants for electronic materials Do.

Hereinafter, a method for selectively producing di-styrene-based phenol using zirconium oxide solid acid catalyst prepared by impregnating zirconium hydroxide according to the present invention with an aqueous sulfuric acid solution will be described in more detail. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In addition, the unit of the additives not specifically described in the specification may be% by weight.

[Property evaluation method]

Gas Chromatography (GC, HP-6890, Hewlett-Packard) analysis was performed to confirm the composition ratios. The conversion rates of phenolic compounds and styrene monomers, MSP, DSP, and TSP in the alkylation reaction of styrene monomer and phenol compound Were calculated according to the following equations (1) and (2).

- GC analysis conditions

GC; HP-6890 (Hewlett-Packard)

Sampling; 5 [mu] l (30 wt% toluene solution)

Carrier gas; He, 1 ml min -1

Column; Capillary column HP-5

Oven tem. ; 100 ℃ → 10 ℃ / min ↑ → 130 ℃ → 18 ℃ / min ↑ → 300 ℃ (15min Hold)

Injection tem. ; 300 ° C

Detector tem. ; 300 ° C (FID)

Split ratio; 1/50

[Formula 1]

[Formula 2]

[Preparation Example 1] Preparation of catalyst using zirconium hydroxide

Aqueous solution of sulfuric acid _{(1M-H 2 SO 4)} 10.8 ml for Zr (OH) ₄ (average particle size: 40㎛) 20g was then impregnated by stirring for 3 hours. After filtration to obtain a solid catalyst, it was dried at 110 ° C for 12 hours and then calcined at 600 ° C for 2 hours to prepare a zirconium oxide solid acid catalyst (5-SO ₄ ^2- / ZrO ₂ ) impregnated with sulfate ions .

[Preparation Example 2] Preparation of catalyst using zirconium oxide

20 g of ZrO ₂ (average particle size: 50 탆) was added to 10.8 ml of an aqueous sulfuric acid solution (1M-H ₂ SO ₄ ) by stirring for 3 hours. After filtration to obtain a solid catalyst, it was dried at 110 ° C for 12 hours and then calcined at 600 ° C for 2 hours to prepare a zirconium oxide solid acid catalyst (5-SO ₄ ^2- / pureZrO ₂ ) impregnated with sulfate ions .

[Example 1]

After replacing the 100cc Schlenk tube with nitrogen, the reaction temperature was adjusted to 100 ° C using a thermostat and a thermocouple (Al / Cr). 10.0 g (0.106 mol) of phenol, 22.0887 g (0.212 mol) of styrene and 5-SO ₄ ^2- / ZrO ₂ catalyst were added in an amount of 5 wt% based on the mixture of phenol and styrene and stirred for 6 hours. After stirring, the catalyst was filtered to give the product.

[Example 2]

(1-SO ₄ ^2- / ZrO ₂ ) was used in the preparation of the SO ₄ ^2- / ZrO ₂ catalyst in Example 1 except that the sulfuric acid ion concentration in the sulfuric acid aqueous solution was 1% by weight To obtain di-styrenated phenol.

[Example 3]

The procedure of Example 1 was repeated except that the sulfuric acid ion concentration of the sulfuric acid ion concentration in the sulfuric acid ion concentration of 3 wt% was used (3-SO ₄ ^2- / ZrO ₂ ) in the production of the SO ₄ ^2- / ZrO ₂ catalyst in Example 1 To obtain di-styrenated phenol.

[Example 4]

(7-SO ₄ ^2- / ZrO ₂ ) in which the sulfuric acid ion concentration of the sulfuric acid ion concentration in the aqueous sulfuric acid solution was 7% by weight in the preparation of the SO ₄ ^2- / ZrO ₂ catalyst in Example 1 was carried out in the same manner as in Example 1 To obtain di-styrenated phenol.

[Example 5]

(15-SO ₄ ^2- / ZrO ₂ ) was used in the preparation of the SO ₄ ^2- / ZrO ₂ catalyst in Example 1 except that the sulfuric acid ion concentration in the aqueous sulfuric acid solution was 15% by weight To obtain di-styrenated phenol.

[Example 6]

A di-styrenated phenol was obtained in the same manner as in Example 1, except that the SO ₄ ^2- / ZrO ₂ catalyst was added in an amount of 1 wt% based on the mixture of phenol and styrene in Example 1.

[Example 7]

A di-styrenated phenol was obtained in the same manner as in Example 1, except that the SO ₄ ^2- / ZrO ₂ catalyst was added in an amount of 3 wt% based on the mixture of phenol and styrene in Example 1.

[Example 8]

A di-styrenated phenol was obtained in the same manner as in Example 1, except that the SO ₄ ^2- / ZrO ₂ catalyst was added in an amount of 7 wt% based on the mixture of phenol and styrene in Example 1.

[Example 9]

A di-styrenated phenol was obtained in the same manner as in Example 1 except that the temperature was changed to 60 DEG C in the production of di-styrenated phenol in Example 7.

[Example 10]

In Example 7, di-styrenated phenol was obtained in the same manner as in Example 1, except that the temperature of the di-styrenated phenol was adjusted to 80 ° C.

[Example 11]

A di-styrenated phenol was obtained in the same manner as in Example 1 except that the temperature of the di-styrenated phenol was adjusted to 120 ° C in Example 7.

[Example 12]

A di-styrenated phenol was obtained in the same manner as in Example 1 except that the temperature was changed to 170 DEG C in the production of di-styrenated phenol in Example 7.

[Comparative Example 1]

In Example 1, SO ₄ ^2- / ZrO ₂ The procedure of Example 1 was repeated except that the catalyst prepared in Preparation Example 2 was used in place of the catalyst to obtain di-styrenated phenol.

[Comparative Example 2]

In Comparative Example 1, SO ₄ ^2- / ZrO ₂ Di-styrenated phenol was obtained in the same manner as in Example 1, except that 15% by weight of sulfuric acid ion concentration in the aqueous solution of sulfuric acid was used in the preparation of the catalyst (15-SO ₄ ^2- / pureZrO ₂ ).

[Comparative Example 3]

A di-styrenated phenol was obtained in the same manner as in Example 1, except that a phosphoric acid catalyst was used in place of the SO ₄ ^2- / ZrO ₂ solid acid catalyst in Example 1.

[Comparative Example 4]

A di-styrenated phenol was obtained in the same manner as in Example 1 except that a sulfuric acid catalyst was used in place of the SO ₄ ^2- / ZrO ₂ solid acid catalyst in Example 1.

[Comparative Example 5]

A di-styrenated phenol was obtained in the same manner as in Example 1, except that a nitric acid catalyst was used instead of the SO ₄ ^2- / ZrO ₂ solid acid catalyst in Example 1.

Conversion Rate (%) Selectivity (%) phenol Styrene MSP DSP TSP Example 1 99.99 99.99 20.2 58.7 21.2 Example 2 44.30 59.70 88.1 10.9 1.0 Example 3 99.80 99.99 24.5 48.8 26.7 Example 4 99.80 99.99 30.2 52.5 17.3 Example 5 99.99 99.99 25.1 53.5 21.4 Example 6 99.98 99.99 30.1 53.4 16.5 Example 7 99.99 99.98 12.9 61.4 25.7 Example 8 99.99 99.99 13.7 52.7 33.6 Example 9 63.20 89.20 54.6 33.8 11.6 Example 10 99.99 99.99 18.3 63.5 18.1 Example 11 99.99 99.99 15.8 60.4 23.7 Example 12 99.99 99.99 12.0 64.4 13.6 Comparative Example 1 43.50 84.60 66.4 29.6 4.0 Comparative Example 2 99.99 99.86 23.6 52.1 24.2 Comparative Example 3 97.31 98.32 76.8 17.2 6.0 Comparative Example 4 98.08 99.69 75.3 21.5 3.2 Comparative Example 5 96.98 98.27 70.7 20.3 9.0

As shown in Table 1, it was confirmed that the selectivity of the di-styrenated phenols of Examples 1 to 12 was high.

As shown in FIG. 2, in Examples 1 to 5, the conversion ratio of the phenol compound to the styrene monomer was almost close to 100% as the sulfuric acid ion concentration of the aqueous sulfuric acid solution was increased. Further, as shown in FIG. 3, the conversion rates of the phenol compound and the styrene monomer were almost close to 100% in Example 1 and Examples 6 to 8 as the catalyst content was increased. As shown in FIG. 4, in Example 1, Example 9, and Example 12, the conversion ratio of the phenol compound and the styrene monomer both approaches nearly 100% as the reaction temperature increases.

(MSP), di-styrenated phenol (DSP), and tri-styrenedione phenol (TSP) were determined according to the sulfate ion concentration of the aqueous sulfuric acid solution in Examples 1 to 4 , It was confirmed that the degree of di-styreneide selectivity was high. As shown in FIG. 1, the zirconium oxide solid acid catalyst of the present invention is a 3-SO ₄ ^2- / ZrO ₂ catalyst having a tetragonal system and a monoclinic system with a crystal structure of 40:60, 5-SO ₄ ^{2 -} / ZrO ₂ catalyst was mixed with tetragonal system and monoclinic system at 44:56. Accordingly, when the concentration of the aqueous sulfuric acid solution is 3 to 6 wt%, the zirconium oxide solid acid catalyst has a mixed crystal structure of a monoclinic system and a tetragonal system so that the activity of the catalyst is high and the selectivity of the di-styrenated phenol (DSP) Respectively.

(MSP), di-styrenated phenol (DSP) and tri-styrenedione phenol (TSP) were confirmed according to the catalyst content in Example 1 and Examples 6 to 8 , It was confirmed that the degree of di-styreneide selectivity was high.

(MSP), di-styrenated phenol (DSP) and tri-styrenedione phenol (TSP) were determined according to the reaction temperatures in Examples 1, 9 and 12 When confirmed, it was confirmed that the degree of selectivity of di-styrenated phenol was high. Further, as shown in FIG. 4, when the reaction temperature is 70 to 100 ° C., styrene-phenol is excellent in hue and is more preferable because it can be applied as a surfactant.

When the Comparative Examples 1 to 2 and the Examples were compared, the conversion rate of the phenol compound and the styrene monomer was low, and the degree of di-styreneide selectivity was increased as the concentration of the sulfuric acid aqueous solution was increased. It was confirmed that the reaction was possible under low mild conditions and the selectivity of di-styrene was also high.

In addition, when Comparative Examples 3 to 4 and Examples were compared, it was confirmed that the selectivity of di-styrenated phenol was low and the conversion rate was lowered in the production using sulfuric acid, phosphoric acid and nitric acid which are liquid acid catalysts other than the solid acid catalyst . Further, after the reaction was carried out using a liquid acid catalyst, further processing was carried out in order to remove the waste acid, wastewater and byproducts, which was troublesome.

The styrene-based phenol (SPs) of the present invention can be used as an important raw material for a color filter of a LCD panel and a developer for a thin film transistor (TFT) as a nonionic surfactant. At this time, the developer is used to develop a photosensitizer for forming a pattern on a glass or plastic surface in the manufacturing process of a TFT-LCD, and is generally formed by mixing distilled water, a hydroxide and a surfactant. In this case, the surfactant should be free of residual phenol, and the higher the content of di-styrenedephenol is, the more applicable it is.

Accordingly, the highly selective preparation method of the di-styrenated phenol of the present invention can increase the selectivity of the di-styrenated phenol, and the di-styrenated phenol can play a hydrophobic role of the surfactant and can be applied to a stable surfactant have.

As described above, in the present invention, a method for selectively producing di-styrene-substituted phenol using zirconium oxide solid acid catalyst prepared by impregnating aqueous solution of zirconium hydroxide with sulfuric acid through the specified matters and the limited embodiments has been described. It is to be understood that the invention is not limited to the above-described embodiment, and that various modifications and changes may be made thereto by those skilled in the art to which the present invention pertains.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (10)

Impregnating the zirconium hydroxide with an aqueous sulfuric acid solution and drying the zirconium hydroxide impregnated with the sulfate ion at 100 to 150 ° C for 10 to 20 hours;
Preparing a zirconium oxide solid acid catalyst having a crystal structure in which a monoclinic system and a tetragonal system are mixed by calcining at 500 to 700 ° C for 1 to 6 hours; And
Preparing a compound represented by the following formula (1), which is obtained by reacting a phenol compound represented by the following formula (2) with a styrene monomer in the presence of the zirconium oxide solid acid catalyst,
Wherein the zirconium oxide solid acid catalyst is prepared by adding zirconium hydroxide particles and sulfuric acid ions in an amount of 3 to 6 wt% based on the total weight of the aqueous sulfuric acid solution.
[Chemical Formula 1]

(2)

(In the above Formulas 1 to 2,
R ₁ and R ₂ are each independently selected from hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, a C ₃ -C ₃₀ cycloalkyl group, and a C ₆ -C ₃₀ aryl group. delete The method according to claim 1,
Wherein the crystal structure is a mixture of tetragonal system and monoclinic system having a peak intensity ratio of 40:60 to 70:30 at the time of measurement by X-ray diffraction (XRD) analysis. delete The method according to claim 1,
Wherein the zirconium oxide solid acid catalyst is a zirconium hydroxide particle to which sulfuric acid ions are impregnated. The method according to claim 1,
Wherein the zirconium hydroxide particles have an average particle diameter of 10 to 50 占 퐉. The method according to claim 1,
Wherein the styrene monomer comprises 1 to 3 moles based on 1 mole of the phenol compound. The method according to claim 1,
Wherein the zirconium oxide solid acid catalyst comprises 1 to 20% by weight, based on the mixture of the phenolic compound and the styrene monomer, of di-styrene nitrile phenol. The method according to claim 1,
Wherein the reaction of the phenolic compound with the styrene monomer is carried out at a reaction temperature of 50 to 170 占 폚. The method according to claim 1,
Wherein the mixture of the phenolic compound and the styrene monomer is reacted under an inert gas supply of argon, nitrogen, helium or neon.

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